HRP950045A2 - Hydrogenation catalyst, process for the preparation thereof and hydrogenation process - Google Patents

Hydrogenation catalyst, process for the preparation thereof and hydrogenation process Download PDF

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HRP950045A2
HRP950045A2 HR00310/94-6A HRP950045A HRP950045A2 HR P950045 A2 HRP950045 A2 HR P950045A2 HR P950045 A HRP950045 A HR P950045A HR P950045 A2 HRP950045 A2 HR P950045A2
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iridium
phosphine
acid
phenyl
ethyl
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HR00310/94-6A
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Croatian (hr)
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Felix Spindler
Ulrich Pittelkow
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Ciba Geigy Ag
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    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
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    • B01J31/2404—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring
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    • C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
    • C07C209/44—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of carboxylic acids or esters thereof in presence of ammonia or amines, or by reduction of nitriles, carboxylic acid amides, imines or imino-ethers
    • C07C209/52—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of carboxylic acids or esters thereof in presence of ammonia or amines, or by reduction of nitriles, carboxylic acid amides, imines or imino-ethers by reduction of imines or imino-ethers
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    • B01J2231/60—Reduction reactions, e.g. hydrogenation
    • B01J2231/64—Reductions in general of organic substrates, e.g. hydride reductions or hydrogenations
    • B01J2231/641—Hydrogenation of organic substrates, i.e. H2 or H-transfer hydrogenations, e.g. Fischer-Tropsch processes
    • B01J2231/643—Hydrogenation of organic substrates, i.e. H2 or H-transfer hydrogenations, e.g. Fischer-Tropsch processes of R2C=O or R2C=NR (R= C, H)
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    • B01J2531/0202—Polynuclearity
    • B01J2531/0205—Bi- or polynuclear complexes, i.e. comprising two or more metal coordination centres, without metal-metal bonds, e.g. Cp(Lx)Zr-imidazole-Zr(Lx)Cp
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Abstract

Reaction products of an iridium(III) salt or a hydrate thereof, a diphosphine having secondary phosphine groups and a metal or ammonium chloride, bromide or iodide are excellent hydrogenation catalysts for ketimine. Using chiral diphosphines and prochiral ketimines, diastereoisomeric secondary amines are obtained in high optical yields.

Description

Predmetni izum odnosi se na katalizator koji se dobiva reakcijom iridijeve soli sa difosfinima i alkalnim metalom ili amonijevim halidima, na pripremu postupka za te katalizatore i na postupak za hidrogenizaciju imina, naročito u prisustvu jedne kiseline. The present invention relates to a catalyst obtained by the reaction of an iridium salt with diphosphines and an alkali metal or ammonium halides, to the preparation of a process for these catalysts and to a process for the hydrogenation of imines, especially in the presence of an acid.

US-A-4 994,615 opisuje postupak za asimetričnu hidrogenizaciju prokiralniih N-arilketimina, kod koje se koriste iridijevi katalizatori sa ligandima kiralnih difosfina. US-A-5 011,995 opisuje postupak za asimetričnu hidrogenizaciju prokiralnih N-alkilketimina, uz korištenje istih katalizatora. US-A-5 112,999 opisuje spojeve polinuklearnog iridija i kompleksne soli iridija, koje sadrže ligande dofosfina, kao katalizatore za hidrogenizaciju imina. Katalizatori se dobivaju reakcijom kompleksa iridijevog olefina i iridijevog diolefina sa difosfinima. US-A-4 994,615 describes a process for the asymmetric hydrogenation of prochiral N-arylketimines using iridium catalysts with chiral diphosphine ligands. US-A-5 011,995 describes a process for the asymmetric hydrogenation of prochiral N-alkylketimines, using the same catalysts. US-A-5 112,999 describes polynuclear iridium compounds and complex iridium salts containing dophosphine ligands as catalysts for imine hydrogenation. Catalysts are obtained by reacting complexes of iridium olefin and iridium diolefin with diphosphines.

Ti postupci homogene katalize pokazali su se dobrima, iako je očito, naročito u slučaju relativno velikih količina ili na industrijskoj razini, da katalizatori često naginju tome, da u manjem ili većem opsegu postanu dezaktivirani, ovisno o prekursoru katalizatora, supstratu i ligandima difosfina koji se koriste. U mnogim slučajevima, naročito na povišenim temperaturama - na primjer na temperaturama nižim od 25°C koje su potrebne za kratko reakcijsko vrijeme - nije moguće postići kompletnu konverziju. Za industrijsku primjenu postupka hidrogenizacije je stoga produktivnost katalizatora premala sa stanovišta gospodarstvene održivosti. These processes of homogeneous catalysis have proven to be good, although it is obvious, especially in the case of relatively large quantities or on an industrial scale, that catalysts often tend to become deactivated to a lesser or greater extent, depending on the catalyst precursor, the substrate and the diphosphine ligands that are used. use. In many cases, especially at elevated temperatures - for example at temperatures lower than 25°C which are necessary for a short reaction time - it is not possible to achieve complete conversion. For the industrial application of the hydrogenation process, the productivity of the catalyst is therefore too low from the point of view of economic sustainability.

Daljnji nedostatak je činjenica, da su početni materijali za katalizatore - kompleksi iridijevog olefina i iridijevog diolefina - nestabilni i skupi, s rezultatom, da je u praksi nemoguće dobiti komercijalne količine. A further disadvantage is the fact that the starting materials for catalysts - complexes of iridium olefin and iridium diolefin - are unstable and expensive, with the result that in practice it is impossible to obtain commercial quantities.

Sad je iznenađujuće pronađeno, da se aktivni homogeni iridijevi katalizatori mogu dobiti iz običnih iridijevih soli, koje su znatno ekonomičnije, reakcijom tih soli sa difosfinima u prisustvu metalnog halida, naročito alkalnog metala ili amonijevog halida. It has now surprisingly been found that active homogeneous iridium catalysts can be obtained from ordinary iridium salts, which are much more economical, by reacting these salts with diphosphines in the presence of a metal halide, especially an alkali metal or ammonium halide.

Također je iznenađujuće pronađeno, da se aktivnost katalizatora može povisiti, ako za vrijeme hidrogenizacije, reakcijska mješavina osim katalizatora, posjeduje i jednu kiselinu. Također je neočekivano pronađeno, da se istovremeno dezaktiviranje katalizatora može znatno smanjiti ili u cijelosti eliminirati. It was also surprisingly found that the activity of the catalyst can be increased if, during hydrogenation, the reaction mixture, in addition to the catalyst, also contains an acid. It was also unexpectedly found that the simultaneous deactivation of the catalyst can be significantly reduced or completely eliminated.

Izum se odnosi na iridijeve spojeve koji se mogu dobiti reakcijom iridijeve(III) ili iridijeve(IV) soli ili njenih hidrata i difosfina sa sekundarnom fosfinskom grupom u prisustvu metalnog klorida, bromida, jodida ili amonijevog klorida, bromida ili jodida. The invention relates to iridium compounds that can be obtained by the reaction of iridium(III) or iridium(IV) salts or their hydrates and diphosphine with a secondary phosphine group in the presence of metal chloride, bromide, iodide or ammonium chloride, bromide or iodide.

Iridijeve(III) soli ili njihovi hidrati, mogu biti primjerice formule I Iridium(III) salts or their hydrates can be, for example, formula I

[image] [image]

u kojoj je X n-valentni anion jedne kiseline, n je 1, 2 ili 3, a in which X is the n-valent anion of one acid, n is 1, 2 or 3, a

m je 0 ili cijeli broj ili frakcija veća od 0 i do 8. m is 0 or an integer or fraction greater than 0 and up to 8.

Iridijeve(IV) soli ili njihovi hidrati mogu napr. biti formule Ia Iridium(IV) salts or their hydrates can e.g. be of formula Ia

[image] [image]

u kojoj where

X' je halogen, naročito F, Cl ili Br, X' is halogen, especially F, Cl or Br,

M2⊕ je dva H⊕, dva katjona alkalnog metala, na primjer Li⊕, Na⊕ ili K⊕ ili kation zemnoalkalnog metala, napr. Mg2⊕, Ca2⊕, Sr2⊕ ili Ba2⊕, a M2⊕ is two H⊕, two alkali metal cations, for example Li⊕, Na⊕ or K⊕, or an alkaline earth metal cation, e.g. Mg2⊕, Ca2⊕, Sr2⊕ or Ba2⊕, a

m je 0 ili cijeli broj ili frakcija veća od 0 i do 8. m is 0 or an integer or fraction greater than 0 and up to 8.

U formulama I i/ili Ia n je uglavnom 1, a m je uglavnom 0 ili cijeli broj ili frakcija veća od 0 i do 4. In formulas I and/or Ia, n is generally 1 and m is generally 0 or an integer or fraction greater than 0 and up to 4.

Anion X može se izvesti iz organskih ili anorganskih kiselina. Primjeri organskih kiselina su alifatske i aromatske karboksilne kiseline, sulfonske kiseline i fosforne kiselina, koje sadrže od 1 do 12, uglavnom od 1 do 8, a naročito od 1 do 4 atoma ugljika i nesupstituirani su ili supstituirani sa F ili Cl. Neki specifični primjeri su mravlja, octena, propionska, maslačna, mono-, d- ili tri-kloro- ili mono-, di- ili tri-fluoro-octena kiselina benzoeva kiselina, feniloctena kiselina, metil-, fenil- ili benzil-fosfonska kiselina i metil-, fenil-, benzil- p-toluil- ili trifluorometil-sulfonska kiselina. Primjeri anorganskih kiselina su kiseline hidrohalida, tetrafluorborna kiselina, tetrafenilborna kiselina, heksafluoro-fosforna, -aresenska-, antimonska, i -bizmutska kiseline, te oksi-kiseline elemenata N, P, S, F, Cl, Br i I. Specifični primjer su HCl, HBr, HI, HF4, HB(fenil)4, HPF6, HSbCl6, HASF6, HSbF6, HClO4, HBrO4, HIO4, H2SO3, H2SO4, HNO2, HNO3, H3PO3 i H3PO4. Anion X can be derived from organic or inorganic acids. Examples of organic acids are aliphatic and aromatic carboxylic acids, sulfonic acids and phosphoric acids, which contain from 1 to 12, mostly from 1 to 8, and especially from 1 to 4 carbon atoms and are unsubstituted or substituted with F or Cl. Some specific examples are formic, acetic, propionic, butyric, mono-, d- or tri-chloro- or mono-, di- or tri-fluoro-acetic acid, benzoic acid, phenylacetic acid, methyl-, phenyl- or benzyl-phosphonic acid acid and methyl-, phenyl-, benzyl-p-toluyl- or trifluoromethyl-sulfonic acid. Examples of inorganic acids are hydrohalide acids, tetrafluoroboric acid, tetraphenylboric acid, hexafluoro-phosphoric, -arsenic-, antimonic, and -bismuth acids, and oxy-acids of the elements N, P, S, F, Cl, Br and I. Specific examples are HCl, HBr, HI, HF4, HB(phenyl)4, HPF6, HSbCl6, HASF6, HSbF6, HClO4, HBrO4, HIO4, H2SO3, H2SO4, HNO2, HNO3, H3PO3 and H3PO4.

Preferirane kiseline iz kojih se može izvesti XnӨ u formuli I, su HCl, HBr, HI, H2SO4, HCIO4, HCIO3, HBrO4, HIO4, HNO3, H3PO3, H3PO4, CF3SO3H, C6H5SO3H, CF3COOH i CCI3COOH. Kod posebnog oblika, XnӨ u formuli I je monovalentni anion (n je uglavnom 1), naročito halid, a najčešće ClӨ. Sol iridija(III) formule I je uglavnom IrCl3.⋅mH2O, gdje je m broj od 1 do 4. Preferred acids from which XnШ in formula I can be derived are HCl, HBr, HI, H2SO4, HCIO4, HCIO3, HBrO4, HIO4, HNO3, H3PO3, H3PO4, CF3SO3H, C6H5SO3H, CF3COOH and CCI3COOH. In a special form, XnШ in formula I is a monovalent anion (n is mostly 1), especially a halide, and most often ClШ. The iridium(III) salt of formula I is mostly IrCl3.⋅mH2O, where m is a number from 1 to 4.

Uglavnom, svi halogeni spojevi metala glavnih grupa i podgrupa Periodične tabele elemenata mogu se koristiti kao metalni halidi, pod uvjetom da su topivi u reakcijskoj mješavini i ne djeluju kao oksidirajuća sredstva prema drugim reaktantima u reakcijskoj mješavini. Prednost se daje korištenju metalnih halida. Basically, all halogen compounds of metals of the main groups and subgroups of the Periodic Table of Elements can be used as metal halides, provided that they are soluble in the reaction mixture and do not act as oxidizing agents towards other reactants in the reaction mixture. Preference is given to the use of metal halides.

Kationi metala ili zemnoalkalnog metala u halidima metala i zemnoalkalnih metala uglavnom su Li, Na, K, Rb ili Cs katjoni, naročito Li⊕, Na⊕ i K⊕. Kation amonija u amonijevim halidima može biti NH4⊕; primarni amonij ima uglavnom od 1 do 20 atoma ugljika, sekundarni od 2 do 24 atoma ugljika, tercijarni od 3 do 24 atoma ugljika, a kvarternarni od 4 do 24 atoma ugljika. Prednost se daje kvarternarnom amoniju, naročito formule fenilN⊕ (C1-C6alkil)3, benzilN⊕ (C1-C6alkil)3 ili (C1-C6alkil)4N⊕. Od halida alkalnog metala i amonijevih halida, prednost se daje bromidima, a naročito jodidima. U preferiranom obliku, halidi alkalnih metala i amonijevi halidi su Lil, Nal ili Kl ili (C1-C6 alkil)4NI Tetrabutilamonijevom jodidu se daje naročita prednost. Metal or alkaline earth metal cations in metal and alkaline earth metal halides are mainly Li, Na, K, Rb or Cs cations, especially Li⊕, Na⊕ and K⊕. Ammonium cation in ammonium halides can be NH4⊕; primary ammonium has mostly from 1 to 20 carbon atoms, secondary from 2 to 24 carbon atoms, tertiary from 3 to 24 carbon atoms, and quaternary from 4 to 24 carbon atoms. Preference is given to quaternary ammonium, especially of the formula phenylN⊕ (C1-C6alkyl)3, benzylN⊕ (C1-C6alkyl)3 or (C1-C6alkyl)4N⊕. Of the alkali metal halides and ammonium halides, preference is given to bromides, and especially to iodides. In a preferred embodiment, the alkali metal halides and the ammonium halides are Li1, Na1 or K1 or (C1-C6 alkyl)4NI Tetrabutylammonium iodide is particularly preferred.

Difosfini sa grupom sekundarnih fosfina uglavnom su oni Diphosphines with a secondary phosphine group are mainly those

(d) čije fosfinske grupe su vezane na različite atome ugljika ili lanac ugljika sa 2 do 4 atoma ugljika ili (d) whose phosphine groups are attached to different carbon atoms or a carbon chain with 2 to 4 carbon atoms or

(d) čije fosfinske grupe su vezane ili direktno ili preko mosne grupe -CRaRb- u orto pozicijama ciklopentadienilnog prstena ili je svaka vezana na ciklopentadienilni prsten ferocenila ili (d) whose phosphine groups are attached either directly or via a bridging group -CRaRb- in the ortho positions of the cyclopentadienyl ring or each is attached to the cyclopentadienyl ring of ferrocenyl or

(d) čija je jedna fosfinska grupa vezana na lanac ugljika sa 2 ili 3 atoma ugljika, a druga fosfinska grupa je vezana na atom kisika ili atom dušika, koji je završno vezan na taj lanac ugljika ili (d) whose one phosphine group is attached to a carbon chain with 2 or 3 carbon atoms, and the other phosphine group is attached to an oxygen atom or a nitrogen atom, which is terminally attached to that carbon chain, or

(d) čije fosfinske grupe su vezane na dva atoma kisika ili atome dušika, završno vezane na C2-lanac ugljika; (d) whose phosphine groups are attached to two oxygen atoms or nitrogen atoms, terminally attached to the C2 carbon chain;

sa rezultatom, da je u slučajevima (a), (b), (c) i (d) prsten sa 5, 6 ili 7 članova formiran zajedno sa Ir atomom, a Ra i Rb su neovisno jedan od drugoga vodik, C1-C8alkil, C1-C4fluoroalkil, fenil ili benzil ili su fenil ili benzil sa 1 do 3 supstituenata C1-C4alkila ili C1-C4alkoksila. Rb, je uglavnom vodik. Ra je uglavnom C1-C4alkil, a naročito metil. with the result that in cases (a), (b), (c) and (d) a ring with 5, 6 or 7 members is formed together with an Ir atom, and Ra and Rb are independently hydrogen, C1-C8 alkyl , C 1 -C 4 fluoroalkyl, phenyl or benzyl or is phenyl or benzyl with 1 to 3 C 1 -C 4 alkyl or C 1 -C 4 alkoxy substituents. Rb, is mostly hydrogen. Ra is mainly C1-C4alkyl, especially methyl.

Difosfin sadrži obično najmanje jedan atom kiralnog ugljika, a naročito optički čisti stereoizomer (enantiomer ili diastereoizomer) ili par diastereoizomera, jer korištenje katalizatora koji sadrže te ligande dovodi do optičke indukcije kod reakcija hidrogenizacije. Diphosphine usually contains at least one chiral carbon atom, and especially an optically pure stereoisomer (enantiomer or diastereoisomer) or a pair of diastereoisomers, because the use of catalysts containing these ligands leads to optical induction in hydrogenation reactions.

Fosfinske grupe sadrže uglavnom dva identična ili različita, uglavnom identična, nesupstituirana ili supstituirana radikala ugljika sa 1 do 20, naročito od 1 do 12 atoma ugljika. Prednost se daje difosfinima kod kojih grupe sekundarnih difosfina sadrže dva identična ili različita radikala od sljedeće grupe: linearni ili razgranati C1-C12alkil; nesupstituirani ili C1-C6alkilom ili C1-C6alkoksilom supstituirani C5-C12cikloalkil-CH2-, fenil ili benzil, te fenil ili benzil supstituiran sa halogenom (napr. F, Cl ili Br), C1-C6haloalkilom, (C1-C12alkil)3Si, (C6H5)3Si, C1-C6haloalkoksilom (napr. trifluorometoksil), -NH2, fenil2N-, benzil2N-, morfolinilom, piperidinilom, pirolidinilom,(C1-C12alkil)2N-, -amonij-X1Ө, -SO3M1, -CO2M1, -PO3M1 ili sa -COO-C1C6alkilom (napr. -COOCH3), gdje je M1 alkalni metal ili vodik, a X1Ө je anion monobazične kiseline. M je uglavnom H, Li, Na ili K. A1Ө, kao anion monobazične kiseline je uglavnom CLӨ, BrӨ ili anion karboksilne kiseline, na primjer formijat, trokloroacetat ili trifluoroacetat. Phosphine groups contain mainly two identical or different, mainly identical, unsubstituted or substituted carbon radicals with 1 to 20, especially from 1 to 12 carbon atoms. Preference is given to diphosphines in which the secondary diphosphine groups contain two identical or different radicals from the following group: linear or branched C1-C12 alkyl; unsubstituted or C1-C6alkyl or C1-C6alkyl-substituted C5-C12cycloalkyl-CH2-, phenyl or benzyl, and phenyl or benzyl substituted with halogen (e.g. F, Cl or Br), C1-C6haloalkyl, (C1-C12alkyl)3Si, ( C6H5)3Si, C1-C6haloalkyl (e.g. trifluoromethoxy), -NH2, phenyl2N-, benzyl2N-, morpholinyl, piperidinyl, pyrrolidinyl, (C1-C12alkyl)2N-, -ammonium-X1Ш, -SO3M1, -CO2M1, -PO3M1 or with -COO-C1C6alkyl (eg -COOCH3), where M1 is an alkali metal or hydrogen, and X1Ш is an anion of a monobasic acid. M is generally H, Li, Na or K. A1Ш, as an anion of a monobasic acid is generally CLШ, BrШ or an anion of a carboxylic acid, for example formate, trichloroacetate or trifluoroacetate.

Grupa sekundarnih fosfina također može biti radikal formule A secondary phosphine group can also be a radical of the formula

[image] [image]

u kojoj su m i n neovisno jedan od drugoga cijeli broj od 2 do 10, a suma m + n je od 4 do 12, uglavnom od 5 do 8. Primjeri za to su [3.3.1]- i [4.2.1]-fobil formule in which m and n are independently of each other an integer from 2 to 10, and the sum of m + n is from 4 to 12, mostly from 5 to 8. Examples of this are [3.3.1]- and [4.2.1]-fobil formulas

[image] [image]

Primjeri alkila koji uglavnom sadrže od 1 do 16 atoma ugljika su metil, etil, n-propil, izopropil, n-, izo- i tert-butil i izomeri pentila i heksila. Primjeri nesupstituiranog ili alkilom supstituiranog cikloalkila su ciklopentil, cikloheksil, metil- ili etil-cikloheksil i dimetilcikloheksil. Primjeri alkilom, alkoksilom ili haloalkoksilom supstituiranog fenila i metila su metilfenil, dimetilfenil, trimetilfenil, etilfenil, metilbenzil, metoksifenil, dimetoksifenil, trifluorometilfenil, bis-tri-fluorometilfenil, tris-trifluorometoksifenil i bis-trifluorometoksifenil. Preferirane fosfinske grupe su one, koje sadrže iste ili različite, uglavnom iste radikale iz grupe C1-C6 alkila; ciklopentila i cikloheksila koji je nesupstituiran i ima od 1 do 3 C1-C4alkil ili C1-C4alkoksi supstituenata, benzil i, naročito fenil koji je nesupstituiran ili ima od 1 do 3 C1-C4alkoksi, F, Cl, C1-C4fluoroalkil ili C1-C4fluoroalkoksi supstituenata. Examples of alkyls that mainly contain from 1 to 16 carbon atoms are methyl, ethyl, n-propyl, isopropyl, n-, iso- and tert-butyl and isomers of pentyl and hexyl. Examples of unsubstituted or alkyl-substituted cycloalkyl are cyclopentyl, cyclohexyl, methyl- or ethyl-cyclohexyl and dimethylcyclohexyl. Examples of phenyl and methyl substituted with alkyl, alkoxy, or haloalkyl are methylphenyl, dimethylphenyl, trimethylphenyl, ethylphenyl, methylbenzyl, methoxyphenyl, dimethoxyphenyl, trifluoromethylphenyl, bis-trifluoromethylphenyl, tris-trifluoromethoxyphenyl, and bis-trifluoromethoxyphenyl. Preferred phosphine groups are those containing the same or different, mainly the same radicals from the C1-C6 alkyl group; cyclopentyl and cyclohexyl which is unsubstituted and has from 1 to 3 C1-C4alkyl or C1-C4alkoxy substituents, benzyl and, in particular phenyl which is unsubstituted or has from 1 to 3 C1-C4alkoxy, F, Cl, C1-C4fluoroalkyl or C1-C4fluoroalkoxy of substituents.

Difosfin je uglavnom formule II, Ila, Ilb, IIc ili Ild, Diphosphine is mainly of formula II, Ila, Ilb, IIc or Ild,

R7R8P-R9-PR10R11 (II), R7R8P-R9-PR10R11 (II),

R7R8P-0-R12-PR10R11 (IIa), R7R8P-0-R12-PR10R11 (IIa),

R7R8P-NRc-R12-PR10R11 (IIb), R7R8P-NRc-R12-PR10R11 (IIb),

R7R8P-0-R13-0-PR10R11 (IIc), R7R8P-0-R13-0-PR10R11 (IIc),

R7R8P-NRc-R13-NRc-PR10R11 (IId), R7R8P-NRc-R13-NRc-PR10R11 (IId),

u kojima su R7, R8, R10 i R11 neovisno jedan od drugih radikali ugljikovodika sa 1 do 10 atoma ugljika, koji je nusupstituiran ili supstituiran sa C1-C6alkilom, C1-C6alkoksilom, halogenom, C1-C6haloalkilom, (C1-C12alkil)3Si, (C6H5)3Si, C1-C6haloalkoksilom, -NH2, fenil2N-, benzil2N-, morfolinilom, piperidinilom, pirolidinilom, (C1-C12alkil)2N-, -amonij X1Ө, -SO3M1, -CO2M1 –PO3M1 ili sa -COO-C1-C6alkilom, gdje je M1 alkalni metal ili vodik, a X1Ө je anion monobazične kiseline; in which R7, R8, R10 and R11 are independently one of the other hydrocarbon radicals with 1 to 10 carbon atoms, which is unsubstituted or substituted with C1-C6alkyl, C1-C6alkyl, halogen, C1-C6haloalkyl, (C1-C12alkyl)3Si, (C6H5)3Si, C1-C6haloalkyl, -NH2, phenyl2N-, benzyl2N-, morpholinyl, piperidinyl, pyrrolidinyl, (C1-C12alkyl)2N-, -ammonium X1Ш, -SO3M1, -CO2M1 –PO3M1 or with -COO-C1- C6alkyl, where M1 is an alkali metal or hydrogen, and X1Ш is an anion of a monobasic acid;

R9 je linearni C2-C4alkilen koji je nesupstituiran ili supstituiran sa C1-C6alkilom, C5- ili C6-cikloalkilom, fenilom, naftilom ili benzilom; 1,2- ili 1,3-cikloalkilen ili -cikloalkenilen, -bicikloalkilen ili -bicikloalkenilen sa 4 do 10 atoma ugljika, od kojih je svaki nesupstituiran ili supstituiran sa C1-C6alkilom, fenilom ili benzilom; 1,2- ili 1,3-cikloalkilen ili -cikloalkenilen, -bicikloalkilen ili -bicikloalkenilen sa 4 do 10 atoma ugljika, od kojih je svaki nesupstituiran ili supstituiran sa C1-C6alkilom, fenilom iili benzilom i u čijim 1- i/ili 1-pozicijama ili u 3-poziciji je vezan metilen ili C2-C4alkiliden; 1,4-butilen supstituiran u 2,3-pozicijama sa R 9 is linear C 2 -C 4 alkylene which is unsubstituted or substituted with C 1 -C 6 alkyl, C 5 - or C 6 -cycloalkyl, phenyl, naphthyl or benzyl; 1,2- or 1,3-cycloalkylene or -cycloalkenylene, -bicycloalkylene or -bicycloalkenylene of 4 to 10 carbon atoms, each of which is unsubstituted or substituted with C1-C6 alkyl, phenyl or benzyl; 1,2- or 1,3-cycloalkylene or -cycloalkenylene, -bicycloalkylene or -bicycloalkenylene with 4 to 10 carbon atoms, each of which is unsubstituted or substituted with C1-C6 alkyl, phenyl or benzyl and in which 1- and/or 1- positions or in the 3-position, methylene or C2-C4alkylidene is attached; 1,4-Butylene substituted in the 2,3-positions with

[image] [image]

sa C1-C6alkilom, fenilom ili benzilom, gdje su R21 i R22 neovisno jedan od drugoga vodik, C1-C6alkil, fenil ili benzil; 3,4- ili 2,4-pirolidinilen ili 2-metilen-pirolidin-4-il, čiji atom vodika je supstituiran sa vodikom, C1-C12alkilom, fenilom, benzilom, C1-C12alkoksikarbonilom, C1-C8acilom ili C C1-C12alkilaminokarbonilom; ili 1,2-fenilen, 2-benzilen, 1,2-ksililen, 1,8-naftilen, 2,3'-dinaftilen ili 2,2'-difenilen, od kojih je svaki nesupstituiran ili supstituiran sa C1-C4alkilom; with C1-C6alkyl, phenyl or benzyl, where R21 and R22 are independently hydrogen, C1-C6alkyl, phenyl or benzyl; 3,4- or 2,4-pyrrolidinylene or 2-methylene-pyrrolidin-4-yl, the hydrogen atom of which is substituted with hydrogen, C1-C12alkyl, phenyl, benzyl, C1-C12alkoxycarbonyl, C1-C8acyl or C1-C12alkylaminocarbonyl; or 1,2-phenylene, 2-benzylene, 1,2-xylylene, 1,8-naphthylene, 2,3'-dinaphthylene or 2,2'-diphenylene, each of which is unsubstituted or substituted with C 1 -C 4 alkyl;

ili R9 je radikal formule or R9 is a radical of the formula

[image] [image]

u kojoj je R14 vodik, C1-C8alkil, C1-C4fluoroalkil, fenil ili fenil sa 1 do 3 C1-C4alkil ili C1-C4alkoksi supstituenta; wherein R 14 is hydrogen, C 1 -C 8 alkyl, C 1 -C 4 fluoroalkyl, phenyl or phenyl with 1 to 3 C 1 -C 4 alkyl or C 1 -C 4 alkoxy substituents;

R12 je linearni C2 ili C3-alkilen koji je nesupstituiran ili supstituiran sa C1-C6alkilom, C5- ili C6-cikloalkilom, fenilom, naftilom ili benzilom; 1,2- ili 1,3-cikloalkilen ili -cikloalkenilen, -bicikloalkilen ili -bicikloalkenilen sa 4 do 10 atoma ugljika, od kojih je svaki nesupstituiran ili supstituiran sa C1-C6alkilom, fenilom ili benzilom; ili 1,2- ili 1,3-cikloalkilen ili -cikloalkenilen, -bicikloalkilen ili -bicikloalkenilen sa 4 do 10 atoma ugljika, od kojih je svaki nesupstituiran ili supstituiran sa C1-C6alkilom, fenilom ili benzilom, i u čijim 1- i/ili 2-pozicijama ili u 3-poziciji je vezan metilen ili C2-C4alkiliden; 3,4- ili 2,4-piirolidinilen ili 3-metilen-pirolidin-4-il, čiji atom dušika je supstituiran sa vodikom, C1-C12alkilom, fenilom, benzilom, C1-C12alkoksikarbonilom, C1-C8acilom ili C1-C12alkilaminokarbonilom; ili 1,2-fenilen, 2-benzilen, 1,2-, 2,3- ili 1,8-naftilen, od kojih je svaki nesupstituiran ili supstituiran sa C1-C4alkilom; R 12 is linear C 2 or C 3 -alkylene which is unsubstituted or substituted with C 1 -C 6 alkyl, C 5 - or C 6 -cycloalkyl, phenyl, naphthyl or benzyl; 1,2- or 1,3-cycloalkylene or -cycloalkenylene, -bicycloalkylene or -bicycloalkenylene of 4 to 10 carbon atoms, each of which is unsubstituted or substituted with C1-C6 alkyl, phenyl or benzyl; or 1,2- or 1,3-cycloalkylene or -cycloalkenylene, -bicycloalkylene or -bicycloalkenylene with 4 to 10 carbon atoms, each of which is unsubstituted or substituted with C1-C6 alkyl, phenyl or benzyl, and in which 1- and/or methylene or C2-C4 alkylidene is attached to the 2-position or in the 3-position; 3,4- or 2,4-pyrrolidinylene or 3-methylene-pyrrolidin-4-yl, whose nitrogen atom is substituted with hydrogen, C1-C12 alkyl, phenyl, benzyl, C1-C12 alkoxycarbonyl, C1-C8 acyl or C1-C12 alkylaminocarbonyl; or 1,2-phenylene, 2-benzylene, 1,2-, 2,3- or 1,8-naphthylene, each of which is unsubstituted or substituted with C1-C4alkyl;

R13 je linearni C2alkilen koji je nesupstituiran ili je supstituiran sa C1-C6alkilom, C5- ili C6-cikloalkilom, fenilom, naftilom ili benzilom; 1,2-cikloalkilen ili -cikloalkenilen, -bicikloalkilen ili -bicikloalkenilen sa 4 do 10 atoma ugljika, od kojih je svaki nesupstituiran ili supstituiran sa C1-C6alkilom, fenilom ili benzilom; 3,4-pirolidinilen, čiji atom dušika je supstituiran sa vodikom, C1-C12alkilom, fenilom, benzilom, C1-C12alkoksikarbonilom, C1-C8acilom ili C1-C12alkilaminokarbonilom; ili 1,2-fenilen koji je nesupstituiran ili supstituiran sa C1-C4alkilom ili je radikal manje od dvije hidroksilne grupe u orto pozicijama mono- ili di-saharida, a R 13 is linear C 2 alkylene which is unsubstituted or substituted with C 1 -C 6 alkyl, C 5 - or C 6 -cycloalkyl, phenyl, naphthyl or benzyl; 1,2-cycloalkylene or -cycloalkenylene, -bicycloalkylene or -bicycloalkenylene of 4 to 10 carbon atoms, each of which is unsubstituted or substituted with C1-C6 alkyl, phenyl or benzyl; 3,4-pyrrolidinylene, whose nitrogen atom is substituted with hydrogen, C1-C12 alkyl, phenyl, benzyl, C1-C12 alkoxycarbonyl, C1-C8 acyl or C1-C12 alkylaminocarbonyl; or 1,2-phenylene which is unsubstituted or substituted with C1-C4alkyl or the radical is less than two hydroxyl groups in the ortho positions of the mono- or di-saccharide, and

Rc je vodik, C1-C4alkil, fenil ili benzil. R c is hydrogen, C 1 -C 4 alkyl, phenyl or benzyl.

R7, R8, R10 i R11 su uglavnom isti ili različiti, uglavnom različiti radikali sljedeće grupe: C1-6alkil; ciklopentil i cikloheksil koji su nesupstituirani ili imaju od 1 do 3 C1-C4alkil ili C1-C4alkoksi supstituenta, benzil, a naročito fenil koji je nesupstituiran ili ima od 1 do 3 C1-C4alkil, C1-C4alkoksi, F, Cl, C1-C4fluoroalkil ili C1-C4fluoro-alkoksi supstituenta. R 7 , R 8 , R 10 and R 11 are substantially the same or different, substantially different radicals of the following group: C 1-6 alkyl; cyclopentyl and cyclohexyl which are unsubstituted or have from 1 to 3 C1-C4alkyl or C1-C4alkoxy substituents, benzyl, and especially phenyl which is unsubstituted or have from 1 to 3 C1-C4alkyl, C1-C4alkoxy, F, Cl, C1-C4fluoroalkyl or a C 1 -C 4 fluoro-alkoxy substituent.

Preferirana podgrupa difosfina oblikovana je formulama A preferred subgroup of diphosphine is formed by the formulas

[image] [image]

[image] [image]

u kojima su in which they are

R15 i R16 neovisno jedan od drugoga vodik, C1-C4 alkil, fenil, benzil ili fenil ili benzil sa 1 do 3 C1-C4 alkil ili C1-C4 alkoksi supstituenta, R15 and R16 are independently hydrogen, C1-C4 alkyl, phenyl, benzyl or phenyl or benzyl with 1 to 3 C1-C4 alkyl or C1-C4 alkoxy substituents,

R14 je vodik, C1-C4 alkil, fenil, benzil ili fenil ili benzil sa 1 do 3 C1-C4 alkil ili C1-C4 alkoksi supstituenta, R14 is hydrogen, C1-C4 alkyl, phenyl, benzyl or phenyl or benzyl with 1 to 3 C1-C4 alkyl or C1-C4 alkoxy substituents,

R17 je vodik, C1-C4alkil, fenil, benzil, C1-C6alkoksi-CO-, C1-C6alkil-CO, fenil-CO-, naftil-CO- ili C1-C4alkilNH-CO-, R17 is hydrogen, C1-C4alkyl, phenyl, benzyl, C1-C6 alkoxy-CO-, C1-C6alkyl-CO, phenyl-CO-, naphthyl-CO- or C1-C4alkylNH-CO-,

A je difosfinska grupa -PR2, u kojoj je R C1-C6alkil, cikloheksil, fenil, benzil ili fenil ili bezil sa 1 do 3 C1-C4alkil, C1-C4alkoksi, -CF3 ili djelomično ili u potpunosti fluorinirana C1-C4 alkoksi supstituenta, a n je 0, 1 ili 2. A is a diphosphine group -PR2, in which R is C1-C6alkyl, cyclohexyl, phenyl, benzyl or phenyl or bezil with 1 to 3 C1-C4alkyl, C1-C4alkoxy, -CF3 or partially or fully fluorinated C1-C4 alkoxy substituents, and n is 0, 1 or 2.

Od tih difosfina naročita prednost se daje kiralno supstituiranim spojevima. Of these diphosphines, particular preference is given to chirally substituted compounds.

Neki primjeri difosfina kojima se daje prednost su sljedeći (Ph je fenil): Some preferred examples of diphosphines are as follows (Ph is phenyl):

[image] [image]

[image] [image]

Prikladne difosfine i difosfinite opisao je na primjer H.B. Kagan u Chiral Ligands for Asymmetric Catalyst, Asymmetric Synthesis, svezak 5, str. 13-23, Academic Press, Inc., N.Y. (1985.). Dobivanje Uganda ferocenil difosfina opisano je na primjer u EP-A-0 564 406, a opisao ih je i T. Hayashi et al. u Buli. Chem. Soc. Jpn., 53, str. 1136-1151. Suitable diphosphines and diphosphinites are described for example by H.B. Kagan in Chiral Ligands for Asymmetric Catalyst, Asymmetric Synthesis, Volume 5, p. 13-23, Academic Press, Inc., N.Y. (1985). The preparation of Uganda ferrocenyl diphosphines is described, for example, in EP-A-0 564 406, and also described by T. Hayashi et al. in Bula. Chem. Soc. Jpn., 53, p. 1136-1151.

Difosfini kojima se daje prednost su: Preferred diphosphines are:

{(R)-1-[(S)-2-difenilfosfino)ferocenil]}etil-di(3,5-dimetil-4-N,N-dipropil-aminofenil)fosfin {(R)-1-[(S)-2-diphenylphosphino)ferrocenyl]}ethyl-di(3,5-dimethyl-4-N,N-dipropyl-aminophenyl)phosphine

{(R)-1-[(S)-2-difenilfosfino)ferocenil]}etil-di(3,5-diiizopropil-4-N,N-dimetil-aminofenil)fosfin {(R)-1-[(S)-2-diphenylphosphino)ferrocenyl]}ethyl-di(3,5-diisopropyl-4-N,N-dimethyl-aminophenyl)phosphine

{(R)-1-[(S)-2-difenilfosfino)ferocenil]}etil-di(3,5-diizopropil-4-N,N-dibenzilil-aminofenil)fosfin {(R)-1-[(S)-2-diphenylphosphino)ferrocenyl]}ethyl-di(3,5-diisopropyl-4-N,N-dibenzylyl-aminophenyl)phosphine

{(R)-1-[(S)-2-difenilfosfino)ferocenil]}etil-di(3,5-dimetil-4-N,N,-dibenzilil-aminofenil)fosfin {(R)-1-[(S)-2-diphenylphosphino)ferrocenyl]}ethyl-di(3,5-dimethyl-4-N,N,-dibenzylyl-aminophenyl)phosphine

{(R)-1-[(S)-2-difenilfosfino)ferocenil]}etil-di(3,5-dimetil-4-(1'-pirolo)-fenil)fosfin {(R)-1-[(S)-2-diphenylphosphino)ferrocenyl]}ethyl-di(3,5-dimethyl-4-(1'-pyrrolo)-phenyl)phosphine

{(R)-1-[(S)-2-difenilfosfino)ferocenil]}etil-di(3,5-dimetil-4-N,N-dipentil-aminofenil)fosfin {(R)-1-[(S)-2-diphenylphosphino)ferrocenyl]}ethyl-di(3,5-dimethyl-4-N,N-dipentyl-aminophenyl)phosphine

{(R)-1-[(S)-2-difenilfosfino)ferocenil]}etil-di(3,5-dimetil-4-N,N-dimetil-aminofenil)fosfin {(R)-1-[(S)-2-diphenylphosphino)ferrocenyl]}ethyl-di(3,5-dimethyl-4-N,N-dimethyl-aminophenyl)phosphine

1,4-bis(difenilfosfino)butan 1,4-bis(diphenylphosphino)butane

{(R)-1-[(S)-2-di(4-metoksifenil)fosfino)ferocenil]}etil-di(3,5-dimetil-4-N,N-dimetilaminofenil)fosfin, a naročito {(R)-1-[(S)-2-di(4-methoxyphenyl)phosphino)ferrocenyl]}ethyl-di(3,5-dimethyl-4-N,N-dimethylaminophenyl)phosphine, and especially

{(R)-1-[(S)-2-difenilfosfino)ferocenil]}etil-di(3,5-dimetil-fenil)fosfin. {(R)-1-[(S)-2-diphenylphosphino)ferrocenyl]}ethyl-di(3,5-dimethyl-phenyl)phosphine.

Izum se odnosi i na postupak za dobivanje iridijevih spojeva, koji obuhvaća reakciju sa drugom, barem ekvimolarnom količinom soli iridija(III) ili iridija(IV) ili njenim hidratom i fosfinom u prisustvu alkalnog metala ili amonijevog klorida, bromida ili jodida. The invention also relates to a process for obtaining iridium compounds, which includes a reaction with another, at least equimolar amount of iridium(III) or iridium(IV) salt or its hydrate and phosphine in the presence of an alkali metal or ammonium chloride, bromide or iodide.

Postupak obuhvaća gore navedeno. Molarni odnos soli iridija(III) ili iridija(IV) ili njenog hidrata prema fosfinu može biti primjerice od 1:1 do 1:1,5, naročito od 1:1 do 1:1,1. Alkalni metal ili amonijev klorid, bromid ili jodid uglavnom se koriste u suvišku temeljeno da iridijevoj soli ili njenom hidratu. Suvišak može biti primjerice do peterostruk, uglavnom do deseterostruk, temeljeno na 1 molu iridijeve soli ili njenom hidratu. The procedure includes the above. The molar ratio of the salt of iridium(III) or iridium(IV) or its hydrate to phosphine can be, for example, from 1:1 to 1:1.5, especially from 1:1 to 1:1.1. Alkali metal or ammonium chloride, bromide or iodide are generally used in excess based on the iridium salt or its hydrate. The excess can be for example up to five times, mostly up to ten times, based on 1 mole of iridium salt or its hydrate.

Postupak se može provesti u prisustvu ili odsustvu otapala. Preporuča se da se koriste ista otapala kao ona koja se koriste kasnije kod hidrogenizacije. Prikladna otapala koja se mogu koristiti sama ili kao mješavina otapala, posebno su dipolarna otapala. Primjeri otapala su: alifatski i aromatski ugljikovodici, kao pentan, heksan, cikloheksan, metilcikloheksan, benzen, toluen i ksilen; alkoholi kao što su metanol, etanol, n- ili izo-propanol, n-, izo- ili tert-butanol, etilen glikol, dietilen glikol, propandioli, monometil eter ili monoetil eter etilen glikola, eteri kao što su dietil eter, dimetil eter dietilen glikola, tetrahidrofuran i dioksan; halogenirani ugljikovodici kao metilen klorid, kloroform, 1,1,2,2-tetrakloroetan i klorobenzen; esteri i laktoni kao etil acetat, butirolakton i valerolakton; amidi kiseline i laktami, kao što su dimetilformamid, dimetilacetamid i N-metilpirolidon, te ketoni kao aceton, dibutil keton, metil izobutil i metoksiaceton. The procedure can be carried out in the presence or absence of a solvent. It is recommended to use the same solvents as those used later in the hydrogenation. Suitable solvents which can be used alone or as a mixture of solvents are, in particular, dipolar solvents. Examples of solvents are: aliphatic and aromatic hydrocarbons, such as pentane, hexane, cyclohexane, methylcyclohexane, benzene, toluene and xylene; alcohols such as methanol, ethanol, n- or iso-propanol, n-, iso- or tert-butanol, ethylene glycol, diethylene glycol, propanediols, monomethyl ether or ethylene glycol monoethyl ether, ethers such as diethyl ether, dimethyl ether diethylene glycol, tetrahydrofuran and dioxane; halogenated hydrocarbons such as methylene chloride, chloroform, 1,1,2,2-tetrachloroethane and chlorobenzene; esters and lactones such as ethyl acetate, butyrolactone and valerolactone; acid amides and lactams, such as dimethylformamide, dimethylacetamide and N-methylpyrrolidone, and ketones such as acetone, dibutyl ketone, methyl isobutyl and methoxyacetone.

Temperatura reakcije može biti primjerice od -20°C do 100°C, uglavnom od 0°C do 80°C, a naročito do 10°C do 70°C. The reaction temperature can be, for example, from -20°C to 100°C, mostly from 0°C to 80°C, and especially from 10°C to 70°C.

Postupak se primjerice može provesti kako slijedi: iridijeva sol ili njen hidrat, difosfin i metal, naročito alkalni metal ili amonijev klorid, bromid ili jodid se izmiješaju, ako je prikladno doda se otapalo i mješavina se miješa dok se ne završi reakcija. Završetak reakcije može se odrediti primjerice kromatografijom, odredivši potrošnju fosfina ili uglavnom spektroskopijom, na primjer pomoću 1H-NMR. Vrijeme reakcije može biti na primjer do 10, općenito do 5, a najčešće do 2 sata. Dobiva se homogena reakcijska mješavina iz koje se korišteno otapalo može odstraniti. Homogeni ostatak može se izolirati ili kasnije koristiti direktno kao homogeni katalizator za hidrogenizacije. For example, the procedure can be carried out as follows: iridium salt or its hydrate, diphosphine and metal, especially alkali metal or ammonium chloride, bromide or iodide are mixed, if appropriate solvent is added and the mixture is stirred until the reaction is complete. The end of the reaction can be determined for example by chromatography, determining the consumption of phosphine or mainly by spectroscopy, for example by means of 1H-NMR. The reaction time can be, for example, up to 10, generally up to 5, and most often up to 2 hours. A homogeneous reaction mixture is obtained from which the used solvent can be removed. The homogeneous residue can be isolated or later used directly as a homogeneous catalyst for hydrogenation.

Iridijevi spojevi dobiveni prema izumu su izuzetno prikladni kao homogeni katalizatori za hidrogenizaciju imina, naročito za asimetričnu hidrogenizaciju prokiralnih i kiralnih imina. Kemijske konverzije su često kompletne i može se postići velika optička količina od preko 70% ili više. The iridium compounds obtained according to the invention are extremely suitable as homogeneous catalysts for the hydrogenation of imines, especially for the asymmetric hydrogenation of prochiral and chiral imines. Chemical conversions are often complete and high optical yields of over 70% or more can be achieved.

Izum se odnosi i na postupak katalitičke hidrogenizacije imina sa vodikom pod povišenim pritiskom u prisustvu iridijevih katalizatora i sa ili bez inertnog otapala, koji postupak obuhvaća korištenje kao katalizatora iridijev spoj prema izumu ili iridijev spoj dobiven prema izumu. The invention also relates to the process of catalytic hydrogenation of imines with hydrogen under elevated pressure in the presence of iridium catalysts and with or without an inert solvent, which process includes using as a catalyst the iridium compound according to the invention or the iridium compound obtained according to the invention.

U preferiranom obliku, u reakcijsku mješavinu se doda amonijev klorid ili klorid, bromid ili jodid alkalnog metala, naročito ako suvišak tih halida nije korišten kod dobivanja katalizatora. In a preferred form, ammonium chloride or an alkali metal chloride, bromide or iodide is added to the reaction mixture, especially if an excess of these halides was not used in the preparation of the catalyst.

U daljnjem naročito preferiranom obliku, reakcijska mješavina dodatno sadrži jednu kiselinu. In a further particularly preferred form, the reaction mixture additionally contains one acid.

[image] grupu. Ako su grupe asimetrično supstituirane i stoga su spojevi sa frupom prokiralnog ketimina, u postupku prema izumu mješavine optičkih izomera ili čistih optičkih izomera mogu se dobiti ako se koriste enantioselektivni ili diastereoselektivni iridijevi katalizatori. Imini mogu sadržavati daljnje kiralne atome ugljika. Slobodne veze u gornjim formulama mogu biti zasićene sa vodikom ili organskim radikalima sa 1 do 22 atoma ugljika ili organskim heteroradikalima koji imaju od 1 do 20 atoma ugljika i najmanje jedan heteroatom iz grupe O, S, N i P. [image] group. If the groups are asymmetrically substituted and are therefore compounds with a prochiral ketimine group, in the process according to the invention mixtures of optical isomers or pure optical isomers can be obtained if enantioselective or diastereoselective iridium catalysts are used. Imines may contain further chiral carbon atoms. The free bonds in the above formulas can be saturated with hydrogen or organic radicals with 1 to 22 carbon atoms or organic heteroradicals having from 1 to 20 carbon atoms and at least one heteroatom from the group O, S, N and P.

[image] od 1 do 22 atoma ugljika ili sekundarnom aminogrupom koja ima od 2 do 40 atoma ugljika. Organski radikali mogu biti supstituirani na primjer sa F, Cl, Br, C1-C4 } haloalkilom, gdje je halogen uglavnom F ili Cl, -CN, -NO2, -CO2H, -CONH2, -SO3H, -PO3H2 ili C1-C12alkil esterima ili amidima ili fenil esterima ili benzil esterima grupa -CO2H, -SO3H i PO3H2. Aldiminske i ketiminske grupe su posebno reaktivne, s rezultatom, da se uz korištenje postupka prema izumu mogu selektivno hidrogenizirati [image] from 1 to 22 carbon atoms or a secondary amino group that has from 2 to 40 carbon atoms. Organic radicals can be substituted for example with F, Cl, Br, C1-C4 } haloalkyl, where the halogen is mainly F or Cl, -CN, -NO2, -CO2H, -CONH2, -SO3H, -PO3H2 or C1-C12alkyl esters or amides or phenyl esters or benzyl esters of the groups -CO2H, -SO3H and PO3H2. Aldimine and ketimine groups are particularly reactive, with the result that they can be selectively hydrogenated using the process according to the invention

[image] aldiminske i ketiminske grupe obuhvaćaju [image] aldimine and ketimine groups include

[image] [image]

Postupak prema izumu naročito je pogodan za hidrogenizaciju aldimina, ketimina i hidrazona sa formiranjem odgovarajućih amina odn. hidrazina. Ketimini su uglavnom N-supstituirani. Preporuča se, da se koriste katalizatori kiralnog iridija i da se hidrogeniraju enantiomerno čisti, kiralni ili prokiralni ketimini, za dobivanje optičkih izomera, pri čemu je optička dobivena količina (enantiomerni suvišak, ee) na primjer veća od 30%, uglavnom veća od 50&%, a dobivene količine mogu biti i veće od 90%. Optičke dobivene količine pokazuju odnos dva formirana steroizomera, čiji odnos može biti na primjer veći od 2:1, a uglavnom veći od 4:1. The process according to the invention is particularly suitable for the hydrogenation of aldimine, ketimine and hydrazone with the formation of corresponding amines or hydrazine. Ketimines are mostly N-substituted. It is recommended to use chiral iridium catalysts and to hydrogenate enantiomerically pure, chiral or prochiral ketimines, to obtain optical isomers, whereby the optical amount obtained (enantiomeric excess, ee) is for example greater than 30%, mostly greater than 50&% , and the obtained quantities can be higher than 90%. The optical quantities obtained show the ratio of the two formed stereoisomers, whose ratio can be, for example, greater than 2:1, and mostly greater than 4:1.

Imini su uglavnom imini formule III Imines are mainly imines of formula III

[image] [image]

koji se hidrogeniraju, da bi se dobili amini formule IV which are hydrogenated to obtain amines of formula IV

[image] [image]

u kojoj je in which it is

R3 uglavnom supstituent i u kojoj je R3 is mostly a substituent and in which it is

R3 linearni ili razgranati C1-C12alkil, cikloalkil koji ima od 3 do 8 atoma ugljika; heterocikloalkil vezan preko atoma ugljika, sa 3 do 8 prstenastih atoma i 1 ili 2 heteroatoma iz grupe O, S i NR6; C7-C16aralkil vezan preko atoma alkilugljika ili C1-C12alkil supstituiran sa spomenutim cikloalkilom ili heterocikloalkilom ili heteroarilom; R 3 linear or branched C 1 -C 12 alkyl, cycloalkyl having from 3 to 8 carbon atoms; heterocycloalkyl linked through a carbon atom, with 3 to 8 ring atoms and 1 or 2 heteroatoms from the group O, S and NR6; C7-C16aralkyl attached via an alkylcarbon atom or C1-C12alkyl substituted with said cycloalkyl or heterocycloalkyl or heteroaryl;

ili gdje je or where it is

R3 C1-C12aril ili C4-C11heteroaril vezan preko prstenastog atoma ugljika i koji ima 1 ili 2 heteroatoma u prstenu; R3 je nesupstituiran ili supstituiran sa -CN, -NO2, F, Cl, C1-C12alkilom, C1-C12alkoksilom, C1-C12alkiltio, C1-C6haloalkilom, -OH, C6-C12arilom ili -ariloksilom ili -ariltio, C7-C16aralkilom ili -aralkoksilom ili -aralkiltio, sekundarnim aminom koji ima od 2 do 24 atoma ugljika, -CONR4R5 ili sa -COOR4, a radikali arila i arilne grupe u aralkilu, aralkoksilu i aralkiltio su nesupstituirane iuli supstituirane sa -CN, -NO2, F, Cl, C1-C4-alkilom, -alkoksilom ili -alkiltio, -OH, CONR4R5 ilj sa -COOR4; R3 C1-C12aryl or C4-C11heteroaryl bonded through a ring carbon atom and having 1 or 2 heteroatoms in the ring; R 3 is unsubstituted or substituted with -CN, -NO 2 , F, Cl, C 1 -C 12 alkyl, C 1 -C 12 alkoxy, C 1 -C 12 alkylthio, C 1 -C 6 haloalkyl, -OH, C 6 -C 12 aryl or -aryloxy or -arylthio, C 7 -C 16 aralkyl or - with aralkyl or -aralkylthio, secondary amine having from 2 to 24 carbon atoms, -CONR4R5 or with -COOR4, and aryl radicals and aryl groups in aralkyl, aralkyl and aralkylthio are unsubstituted or substituted with -CN, -NO2, F, Cl, by C1-C4-alkyl, -alkyloxy or -alkylthio, -OH, CONR4R5 or with -COOR4;

R4 i R5 su neovisno jedan od drugoga vodik, C1-C12alkil, fenil ili benzil ili su R4 and R5 are independently hydrogen, C1-C12alkyl, phenyl or benzyl or are

R4 i R5 zajedno tetra- ili penta-metilen ili 3-oksapentilen; R4 and R5 together are tetra- or penta-methylene or 3-oxapentylene;

R6 ima isto značenje kao R4; R 6 has the same meaning as R 4 ;

R1 i R2 su neovisno jedan od drugoga atom vodika, C1-C12alkil ili cikloalkil sa 3 do 8 prstenastih atoma ugljika, od kojih je svaki nesupstituiran ili supstituiran sa -OH, C1-C12alkoksilom, fenoksilom, benziloksilom, sekundarnim aminom koji ima od 2 do 24 atoma ugljika, -CONR4R5 ili sa -COOR4; C6-C12aril ili C7-C16aralkil koji je nesupstituiran ili supstituiran ka R3 ili -CONR4R5, gdje su R4 i R5 kao što je gore definirano; ili R1 and R2 are, independently of each other, a hydrogen atom, C1-C12alkyl or cycloalkyl with 3 to 8 ring carbon atoms, each of which is unsubstituted or substituted with -OH, C1-C12alkyl, phenoxyl, benzyloxyl, a secondary amine having from 2 to 24 carbon atoms, -CONR4R5 or with -COOR4; C 6 -C 12 aryl or C 7 -C 16 aralkyl which is unsubstituted or substituted by R 3 or -CONR 4 R 5 , where R 4 and R 5 are as defined above; or

R3 je definiran kao gore, a R1 i R2 zajedno su alkilen koji ima 2 do 5 atoma ugljika koji su eventualno prekinuti sa 1 ili 2 -O-, -S- ili NRg radikalima i/ili nesupstituriani ili supstituirani sa =0 ili kao R1 i R2 gore u značenju alkila i/ili kondenzirani sa benzenom, piridinom, pirimidinom, furanom, tiofenom ili pirolom; ili R3 is defined as above, and R1 and R2 together are alkylene having 2 to 5 carbon atoms optionally terminated by 1 or 2 -O-, -S- or NRg radicals and/or unsubstituted or substituted with =0 or as R1 and R 2 above in the meaning of alkyl and/or fused with benzene, pyridine, pyrimidine, furan, thiophene or pyrrole; or

R2 je definiran kao gore, a R1 i R3 su zajedno alkilen koji ima od 2 do 5 atoma ugljika, koji je eventualno prekinut sa 1 ili 2 -0-, -S- ili -NR6-radikala i/ili nesupstituiran ili supstituiran sa =0 ili kao R1 i R2 gore u značenju alkila i/ili kondenziran sa benzenom, piridinom, pirimidinom, furanom, tiofenom ili pirolom. R2 is defined as above, and R1 and R3 together are alkylene having from 2 to 5 carbon atoms, which is optionally terminated by 1 or 2 -O-, -S- or -NR6-radicals and/or unsubstituted or substituted with = 0 or as R1 and R2 above in the meaning of alkyl and/or condensed with benzene, pyridine, pyrimidine, furan, thiophene or pyrrole.

R1 i R2i R3 mogu biti supstituirani u svakoj željenoj poziciji sa identičnim ili različitim radikalima, napr. sa 1 do 5, uglavnom od 1 do 3 supstituenta. R1 and R2 and R3 can be substituted in any desired position with identical or different radicals, e.g. with 1 to 5, mostly 1 to 3 substituents.

Radikali R1 i R2i R3 mogu sadržavati jedan ili više kiralnih centara. Radicals R1 and R2 and R3 may contain one or more chiral centers.

Prikladni supstituenti za R1 i R2 su; C1-C12 uglavnom C1-C6-, a naročito C1-C4 R11alkil, -alkoksil ili -alkiltio, napr. metil, etil, propil, n-, izo- i tert-butil, izomeri pentila, heksila, oktila, nonila, decila, undecila i dodecila, te odgovarajući radikali alkoksila i alkiltio; C1-C5-, uglavnom C1-C4-haloalkil koji kao halogen ima uglavnom F i Cl, napr. trifluoro- ili trikloro-metil, difluoroklorometil, fluorodikloro-metil, 1,1-difluoroet-1-il, 1,1-dikloroet-1-il, 1,1-trikloro- ili 1,1,1-trifluoro-et-2-il, pentakloroetil, pentafluoroetil, 1,1,1-trifluoro-2,2-dikloroetil, n-perfluoropropil, izo-perfluoropropil, n-perfluorobutil, fluoro- ili kloro-metil, difluoro- ili dikloro-metil, 1-fluoro- ili 1-kloro-et-2-il ili -et-1-il, 1-, 2- ili 3-fluoro- ili 1-, 2- ili 3-kloro-prop-1-il ili -prop-2-il ili -prop-3-il, 1-fluoro- ili 1-kloro-but-1-il, -but-2-il, -but-3-il ili -but-4-il, 2,3-dikloro-prop-1-il, 1-kloro-2-fluoro-prop-3-il, 2,3-diklorobut-1-il; C6-C12-aril, -ariloksil ili -ariltio, kod kojih je aril uglavnom naftil, a naročito fenil, C7-C16-aralkil, -aralkoksil i -aralkiltio, kod kojih je radikal arila uglavnom naftil, a naročito fenil, a radikal alkilena je linearan ili razgranat i sadrži od 1 do 10, uglavnom od 1 do 6, a naročito od 1 do 3 atoma ugljika, na primjer benzil, naftilmetil, 1- ili 2-fenil-et-il ili -et-2-il, 1-, 2- ili 3-fenil-prop-1-il, -prop-2-il ili -prop-3-il, gdje se naročita prednost daje benzilu; Suitable substituents for R1 and R2 are; C1-C12 mainly C1-C6-, and especially C1-C4 R11alkyl, -alkyl or -alkylthio, e.g. methyl, ethyl, propyl, n-, iso- and tert-butyl, isomers of pentyl, hexyl, octyl, nonyl, decyl, undecyl and dodecyl, and the corresponding alkyl and alkylthio radicals; C1-C5-, mainly C1-C4-haloalkyl which has mainly F and Cl as halogen, e.g. trifluoro- or trichloro-methyl, difluorochloromethyl, fluorodichloro-methyl, 1,1-difluoroethyl-1-yl, 1,1-dichloroethyl-1-yl, 1,1-trichloro- or 1,1,1-trifluoro-eth- 2-yl, pentachloroethyl, pentafluoroethyl, 1,1,1-trifluoro-2,2-dichloroethyl, n-perfluoropropyl, iso-perfluoropropyl, n-perfluorobutyl, fluoro- or chloro-methyl, difluoro- or dichloro-methyl, 1- fluoro- or 1-chloro-eth-2-yl or -eth-1-yl, 1-, 2- or 3-fluoro- or 1-, 2- or 3-chloro-prop-1-yl or -prop- 2-yl or -prop-3-yl, 1-fluoro- or 1-chloro-but-1-yl, -but-2-yl, -but-3-yl or -but-4-yl, 2,3 -dichloro-prop-1-yl, 1-chloro-2-fluoro-prop-3-yl, 2,3-dichlorobut-1-yl; C6-C12-aryl, -aryloxyl or -arylthio, where the aryl is mostly naphthyl, especially phenyl, C7-C16-aralkyl, -araloxyl and -aralkylthio, where the aryl radical is mostly naphthyl, especially phenyl, and the alkylene radical is linear or branched and contains from 1 to 10, mainly from 1 to 6, and especially from 1 to 3 carbon atoms, for example benzyl, naphthylmethyl, 1- or 2-phenyl-ethyl-yl or -eth-2-yl, 1-, 2- or 3-phenyl-prop-1-yl, -prop-2-yl or -prop-3-yl, where particular preference is given to benzyl;

radikali koji sadrže gore spomenute arilne grupe mogu biti mono- ili polisupstituiran, na primjer sa C1-C4-alkilom, -alkoksilom ili -alkiltio, halogenom, -OH, - CONR4R5 ili sa -COOR5, gdje su R4 i R5 kao što je definirano; primjeri su metil, etil, n- i izo-propil, butil, odgovarajući radikali alkoksila i alkiltio, F, Cl, Br, dimetil-, metil-etil i dietil-karbamoil i metoksi-, etoksi-, fenoksi- i benziloksi-karbonil; the radicals containing the above-mentioned aryl groups can be mono- or polysubstituted, for example with C1-C4-alkyl, -alkyloxy or -alkylthio, halogen, -OH, -CONR4R5 or with -COOR5, where R4 and R5 are as defined ; examples are methyl, ethyl, n- and iso-propyl, butyl, the corresponding alkyl and alkylthio radicals, F, Cl, Br, dimethyl-, methyl-ethyl and diethyl-carbamoyl and methoxy-, ethoxy-, phenoxy- and benzyloxy-carbonyl ;

halogen, uglavnom F i Cl; halogen, mainly F and Cl;

sekundarni amin sa 2 do 24, uglavnom od 2 do 12, a naročito od 2 do 6 atoma ugljika, pri čemu sekundarni amin uglavnom sadrži 2 alkilne grupe, na primjer dimetil-, metiletil-, dietil-, metilpropil-, metil-n-butil, di-n-propil-, di-n-butil, di-n-heksil-amino; secondary amine with 2 to 24, mainly from 2 to 12, and especially from 2 to 6 carbon atoms, whereby the secondary amine mainly contains 2 alkyl groups, for example dimethyl-, methylethyl-, diethyl-, methylpropyl-, methyl-n- butyl, di-n-propyl-, di-n-butyl, di-n-hexyl-amino;

- CONR4R5, kod kojeg su R4 i R5 neovisno jedan od drugoga C1-C12-, uglavnom C1-C6, a naročito C1-C4-alkil ili R4 i R5 su zajedno tetra-ili penta-metilen ili 3-oksapentilen, pri čemu je alkil linearan ili razgranat, napr. dimetil-, metiletil-, dietil-, metil-n-propil-, etil-n-propil-, di-n-propil-, metil-n-butil-, etil-n-butil-, n-propil-n-butil- i di-n-butil-karbamoil; - CONR4R5, where R4 and R5 independently of each other are C1-C12-, mainly C1-C6, and especially C1-C4-alkyl or R4 and R5 together are tetra-or penta-methylene or 3-oxapentylene, where linear or branched alkyl, e.g. dimethyl-, methylethyl-, diethyl-, methyl-n-propyl-, ethyl-n-propyl-, di-n-propyl-, methyl-n-butyl-, ethyl-n-butyl-, n-propyl-n- butyl- and di-n-butyl-carbamoyl;

-COOR4, gdje je R4 C1-C12-, uglavnom C1-C6-alkil, koji može biti linearan ili razgranat, napr. metil, etil, n- i izo-propiil, n-, izo- i tert-butil i izomeri pentila, heksila, heptila, oktila, nonila, decila, undecila i dodecila. -COOR4, where R4 is C1-C12-, mainly C1-C6-alkyl, which can be linear or branched, e.g. methyl, ethyl, n- and iso-propyl, n-, iso- and tert-butyl and isomers of pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl and dodecyl.

R1 i R2i R3 mogu sadržavati naročito funkcionalne grupe kao što su keto grupe, -CN, -NO2, dvostruke veze ugljika, N-O-, grupe aromatskog halogena i grupe amida. R1 and R2 and R3 may contain especially functional groups such as keto groups, -CN, -NO2, carbon double bonds, N-O-, aromatic halogen groups and amide groups.

R1 i R2 kao heteroaril uglavnom su prsten sa 5 ili 6 članova, koji ima 1 ili 2 identična ili različita heteroatoma, naročito O, S ili N, koji sadrži uglavnom 4 ili 5 atoma ugljika i može biti kondenziran sa benzenom. Primjeri heteroaromatika iz kojih se može izvesti R1 su furan, pirol, tiofen, piridin, pirimidin, indol i kvinolin. R1 and R2 as heteroaryl are generally a 5- or 6-membered ring, which has 1 or 2 identical or different heteroatoms, especially O, S or N, which contains mainly 4 or 5 carbon atoms and can be condensed with benzene. Examples of heteroaromatics from which R1 can be derived are furan, pyrrole, thiophene, pyridine, pyrimidine, indole and quinoline.

R1 i R2 kao heteroarilom supstituirani alkil su uglavnom izvedeni iz prstena sa 5 ili 6 članova koji ima 1 ili 2 identična ili različita heteroatoma, naročito O, S ili N, koji sadrži uglavnom 4 ili 5 atoma ugljika i može se kondenzirati sa benzenom. Primjeri heteroaromatika su furan, pirol, tiofen, piridin, pirimidin, indol i kvinolin. R1 and R2 as heteroaryl-substituted alkyl are mainly derived from a 5- or 6-membered ring having 1 or 2 identical or different heteroatoms, especially O, S or N, containing mainly 4 or 5 carbon atoms and can be condensed with benzene. Examples of heteroaromatics are furan, pyrrole, thiophene, pyridine, pyrimidine, indole and quinoline.

R1 i R2 kao heterocikloalkil ili kao heterocikloalkilom supstituirani alkil sadrže uglavnom od 4 do 6 prstenastih atoma i 1 ili 2 identična ili različita heteroatoma iz grupe O, S i NR6 i može biti kondenziran sa benzenom. Može se izvesti na primjer iz pirolidna, tetrahidrofurana, tetrahidrotiofena, indana, pirazolidina, oksazolidina, piperidina, piperazina ili morfolina. R1 and R2 as heterocycloalkyl or as heterocycloalkyl-substituted alkyl contain mainly from 4 to 6 ring atoms and 1 or 2 identical or different heteroatoms from the group O, S and NR6 and can be condensed with benzene. It can be derived for example from pyrrolidine, tetrahydrofuran, tetrahydrothiophene, indane, pyrazolidine, oxazolidine, piperidine, piperazine or morpholine.

R1 i R2i R3 kao alkil su uglavnom nesupstituirani ili supstituirani C1-C6-, naročito C1-C4alkil, koji može biti linearan ili razgranat. Primjeri su metil, etil, izo- i n-propil, izo-, n- i tert-butil, izomeri pentila, heksila, heptila, oktila, nonila, decila, undecila i dodecila. R1 and R2 and R3 as alkyl are mainly unsubstituted or substituted C1-C6-, especially C1-C4alkyl, which can be linear or branched. Examples are methyl, ethyl, iso- and n-propyl, iso-, n- and tert-butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl and dodecyl isomers.

R1 i R2i R3 kao nesupstituirani ili supstituirani cikloalkil sadrže uglavnom od 3 do 6, naročito 5 ili 6 prstenastih atoma ugljika. Primjeri su ciklopropil, ciklobutil, ciklopentil, cikloheksil, cikloheptil i ciklooktil. R1 and R2 and R3 as unsubstituted or substituted cycloalkyl contain mostly from 3 to 6, especially 5 or 6 ring carbon atoms. Examples are cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl.

R1 i R2i R3 kao aril su uglavnom nesupstituirani ili supstituirani naftil, a naročito penil. R1 i R2i R3 kao aralkil su uglavnom nesupstituirani ili supstituirani fenilalkil sa 1 do 10, uglavnom od 1 do 6, a naročito od 1 do 4 atoma ugljika u alkilenu, koji je linearan ili razgranat. Primjeri su naročito benzil i 1-fenilet-1-il, 2-fenilet-1-il, 1-fenilprop-l-il, l-fenilprop-2-il, l-fenilprop-3-il, 2-fenilprop-l-il, 2-fenilprop-2-il i l-fenilbut-4-il. R1 and R2 and R3 as aryl are mostly unsubstituted or substituted naphthyl, especially phenyl. R1 and R2 and R3 as aralkyl are mainly unsubstituted or substituted phenylalkyl with 1 to 10, mainly from 1 to 6, and especially from 1 to 4 carbon atoms in alkylene, which is linear or branched. Examples are especially benzyl and 1-phenyleth-1-yl, 2-phenyleth-1-yl, 1-phenylprop-1-yl, 1-phenylprop-2-yl, 1-phenylprop-3-yl, 2-phenylprop-1 -yl, 2-phenylprop-2-yl and 1-phenylbut-4-yl.

Kod R2 i R3 kao -CONR4R5 i -COOR4, R4 i R5 su uglavnom C1-C6-, naročito C1-C4-alkil ili R4 i R5 su zajedno tetrametilen, pentametilen ili 3-oksapentilen. Primjeri alkila su gore spomenuti. With R2 and R3 as -CONR4R5 and -COOR4, R4 and R5 are mainly C1-C6-, especially C1-C4-alkyl or R4 and R5 together are tetramethylene, pentamethylene or 3-oxapentylene. Examples of alkyl are mentioned above.

R1 i R2 zajedno ili R1 i R3 zajedno kao alkilen, su uglavnom prekinuti sa 1 -0-, -S- ili -NR5- uglavnom -O-. R1 i R2 zajedno ili R1 i R3 zajedno čine, sa atomom ugljika ili sa -N=C grupom na koju su vezani, uglavnom prsten sa 5 ili 6 članova. Za supstituente se primjenjuju gore spomenute prednosti. Kao kondenzirani alkilen, R1 i R2 zajedno ili R1 i R3 zajedno su uglavnom alkilen kondenziran sa benzenom ili piridinom, Primjeri alkilena su: etilen, 1,2- ili 1,3-propilen, 1,2-, 1,3- ili 1,4-butilen, 1,5-pentilen i 1,6-heksilen. Primjeri prekinutih ili =0-supstituiranih alkilena su 2-oksa-1,3-propilen, 2-oksa-1,4-butilen, 2-oksa- ili 3-oksa-1,5-pentilen, 3-tia-1,5-pentilen, 2-tia-1,4-butilen,m 2-tia-1,3-propiIen, 2-metilimino-1,3-propiIen, 2-etilimino-1,4-butilen,2- ili 3-metilimino-1,5-pentilen, 1-okso-2-oksa-1,3-propilen,1-okso-2-oksa-1,4-butilen, 2-okso-3-oksa-1,4-butilen, 1-oksa-2-okso-1,5-pentilen. Primjeri kondenziranog alkilena su: R 1 and R 2 together or R 1 and R 3 together as alkylene, are generally terminated by 1 -O-, -S- or -NR 5 - generally -O-. R1 and R2 together or R1 and R3 together form, with the carbon atom or with the -N=C group to which they are attached, generally a ring with 5 or 6 members. For substitutes, the advantages mentioned above apply. As fused alkylene, R1 and R2 together or R1 and R3 together are generally alkylene fused with benzene or pyridine. Examples of alkylene are: ethylene, 1,2- or 1,3-propylene, 1,2-, 1,3- or 1 ,4-butylene, 1,5-pentylene and 1,6-hexylene. Examples of interrupted or =O-substituted alkylenes are 2-oxa-1,3-propylene, 2-oxa-1,4-butylene, 2-oxa- or 3-oxa-1,5-pentylene, 3-thia-1, 5-pentylene, 2-thia-1,4-butylene, m 2-thia-1,3-propylene, 2-methylimino-1,3-propylene, 2-ethylimino-1,4-butylene, 2- or 3- methylimino-1,5-pentylene, 1-oxo-2-oxa-1,3-propylene, 1-oxo-2-oxa-1,4-butylene, 2-oxo-3-oxa-1,4-butylene, 1-oxa-2-oxo-1,5-pentylene. Examples of condensed alkylene are:

[image] [image]

Primjeri kondenziranog i prekinutog i nesupstituiranon ili =0-supstituiranog alkilena su: Examples of condensed and interrupted and unsubstituted anone or =0-substituted alkylene are:

[image] [image]

R3 i R4 su uglavnom neovisno jedan od drugoga vodik, C1-C4 alkil, fenil ili benzil. R6 je uglavnom vodik ili C1-C4 alkil. R 3 and R 4 are generally independently hydrogen, C 1 -C 4 alkyl, phenyl or benzyl. R6 is generally hydrogen or C1-C4 alkyl.

Daljnja preferirana grupa oblikovana je prokiralnim iminima, kod kojih su u formuli III R1 i R2i R3 svaki različit od drugoga, a R3 nije vodik. A further preferred group is formed by prochiral imines, in which in formula III R 1 and R 2 and R 3 are each different from the other, and R 3 is not hydrogen.

Kod naročito preferirane grupe, u formuli III R3 je 2,6-di- C1-C4 alkilfen-1-il, a naročito 2,6-dimetilfen-1-il ili 2-metil-6-etilfen-1-il, R\ je C1-C4 alkil, a naročito etil ili metil, dok je R2 C1-C4 alkil, C1-C4 alkoksimetil ili C1-C4alkoksietil, a naročito metoksimetil. In a particularly preferred group, in formula III R3 is 2,6-di-C1-C4 alkylphen-1-yl, and especially 2,6-dimethylphen-1-yl or 2-methyl-6-ethylphen-1-yl, R \ is C1-C4 alkyl, especially ethyl or methyl, while R2 is C1-C4 alkyl, C1-C4 alkoxymethyl or C1-C4 alkoxyethyl, especially methoxymethyl.

Od tih su posebno važni imini formule Of these, the imines of the formula are especially important

[image] [image]

kao što je i imin formule such as the imine formula

[image] [image]

Imini formule III su poznati ili se mogu dobiti u skladu sa poznatim postupcima iz aldehida ili ketona i primarnih amina. Imines of formula III are known or can be obtained according to known procedures from aldehydes or ketones and primary amines.

Iridijevi katalizatori mogu se dodati u reakcijsku mješavinu kao izolirani spojevi. No, dobrim se pokazalo, da se katalizatori pripremaju in situ prije reakcije sa ili bez otapala, te da se kasnije koriste direktno za hidrogenizaciju, na primjer tako, da se u katalizator dobiven in situ prvo doda jedna kiselina. Iridium catalysts can be added to the reaction mixture as isolated compounds. However, it turned out to be good that the catalysts are prepared in situ before the reaction with or without a solvent, and that they are later used directly for hydrogenation, for example by first adding an acid to the catalyst obtained in situ.

Iridijevi katalizatori se uglavnom koriste u količinama od 0.001 do 10 molnih postotaka, naročito od 0.001 do 10 molnih %, a najčešće od 0.01 do 5 molnih %, temeljeno na iminu. Iridium catalysts are mainly used in amounts from 0.001 to 10 mole percent, especially from 0.001 to 10 mole %, and most often from 0.01 to 5 mole %, based on the imine.

Molarni odnos imine prema iridijevom katalizatoru može biti na primjer od 1,000,000 prema 10, uglavnom od 500,000 prema 20, a naročito od 300,000 prema 100. The molar ratio of imine to iridium catalyst can be, for example, 1,000,000 to 10, mostly 500,000 to 20, and especially 300,000 to 100.

Postupak se uglavnom provodi na temperaturi od -20 do 100°C, naročito od 0 do 80°C, a najčešće od 10 do 70°C i uglavnom pod pritiskom vodika od 2 x 105 do 1.5 x 107 Pa (od 5 do 150 bara), naročito od 106 do 107 Pa (od 10 do 100 bara). The procedure is mainly carried out at a temperature from -20 to 100°C, especially from 0 to 80°C, and most often from 10 to 70°C and mostly under hydrogen pressure from 2 x 105 to 1.5 x 107 Pa (from 5 to 150 bar ), especially from 106 to 107 Pa (from 10 to 100 bar).

Preporučljivi oblik postupka hidrogenizacije prema izumu obuhvaća dodatno korištenje amonija ili klorida, bromida ili jodida alkalnog metala. Ti kloridi, bromidi i jodidi uglavnom se koriste u količinama od 0.01 do 200 molnih %, naročito od 0.05 do 100 molnih %, a uglavnom od 0.5 do 50 molnih %, temeljeno na iridijevom katalizatoru. Jodidima se daje prednost. Amonij je uglavnom tetraalkilamonij sa 1 do 6 atoma ugljika u alkilnim grupama, a alkalni metal je uglavnom natrij, litij ili kalij. Naročita prednost daje se jodidu tetrabutilamoniju. A recommended form of the hydrogenation process according to the invention includes the additional use of ammonium or alkali metal chloride, bromide or iodide. These chlorides, bromides and iodides are generally used in amounts from 0.01 to 200 mol %, especially from 0.05 to 100 mol %, and mostly from 0.5 to 50 mol %, based on the iridium catalyst. Iodides are preferred. The ammonium is generally tetraalkylammonium with 1 to 6 carbon atoms in the alkyl groups, and the alkali metal is generally sodium, lithium, or potassium. Particular preference is given to tetrabutylammonium iodide.

Reakcija se može provesti u odsustvu ili u prisustvu aprotičnih ili protičnih otapala. Prikladna otapala koja se mogu koristiti sama ili kao mješavina otapala, naročito su aprotična otapala. Primjeri su: The reaction can be carried out in the absence or presence of aprotic or protic solvents. Suitable solvents that can be used alone or as a mixture of solvents are especially aprotic solvents. Examples are:

alifatski i aromatski ugljikovodici, kao što su pentan, heksan, cikloheksan, metilcikloheksan, benzen, toluen i ksilen; eteri kao dietil eter, dietilen glikol, dimetil eter, tetrahidrofuran i dioksa; halogenirani ugljikovodici kao metilen klorid, kloroform, 1,1,2,2-tetrakloroetan i klorobenzen; aliphatic and aromatic hydrocarbons, such as pentane, hexane, cyclohexane, methylcyclohexane, benzene, toluene and xylene; ethers such as diethyl ether, diethylene glycol, dimethyl ether, tetrahydrofuran and dioxa; halogenated hydrocarbons such as methylene chloride, chloroform, 1,1,2,2-tetrachloroethane and chlorobenzene;

esteri i laktoni kao što su etil acetat, butirolakton i valerolakton; esters and lactones such as ethyl acetate, butyrolactone and valerolactone;

amidi kiseline i laktami kao dimetilformamid, dimetilacetamid i N-metilpirolidon, te ketoni kao aceton, dibutil keton, metil izobutil keton i metoksiaceton. acid amides and lactams such as dimethylformamide, dimethylacetamide and N-methylpyrrolidone, and ketones such as acetone, dibutyl ketone, methyl isobutyl ketone and methoxyacetone.

Prikladni su i alkanoli kao metanol, etanol, propanol, butanol ili metoksietanol. Alkanols such as methanol, ethanol, propanol, butanol or methoxyethanol are also suitable.

Poseban oblik postupka prema izumu sadrži dodatn okorištenje jedne kiseline, koja može biti anorganska, ili uglavnom organska kiselina. Kiselina se uglavnom koristi u barem jednakoj molarnoj količini ka iridijev katalizator (jednake katalitičke količine), a može se koristiti i u suvišku. Suvišak može čak biti i kod korištenja kiseline kao otapala. Koristi se uglavnom od 0.1 do 50 tež. postotaka kiseline, temeljeno na nezasićenom organskom spoju. U mnogim slučajevima je od prednosti, da se koriste anhidrirane kiseline. A special form of the process according to the invention contains the additional use of one acid, which can be inorganic or mainly organic acid. The acid is generally used in at least the same molar amount as the iridium catalyst (equal catalytic amounts), and can be used in excess. There can even be an excess when using an acid as a solvent. It is used mainly from 0.1 to 50 wt. acid percentages, based on the unsaturated organic compound. In many cases, it is advantageous to use anhydrous acids.

Neki primjeri anorganskih kiselina su H2SO4, visoko koncentrirana sumporna kiselina (oleura), H3PO4, ortofosforna kiselina, HF, HCl, HBr, HI, HClO4, HBF4, HPF6, HAsF6, HSbCl6, HSbF6 i HB(fenil)4. Prednost se daje H2SO4. Some examples of inorganic acids are H2SO4, highly concentrated sulfuric acid (oleuric acid), H3PO4, orthophosphoric acid, HF, HCl, HBr, HI, HClO4, HBF4, HPF6, HAsF6, HSbCl6, HSbF6, and HB(phenyl)4. H2SO4 is preferred.

Primjeri organskih kiselina su alifatske ili aromatske, eventualn halogenirane (fluorinirane ili klorinirane) karboksilne kiseline, sulfonske kiseline, fosforne(V) kiseline (na primjer fosfonske kiseline, fosfonične kiseline) sa uglavnom od 1 do 20, naročito od 1 do 12, a najčešće od 1 do 6 atoma ugljika. Primjeri su mravlja kiselina, octena kiselina, propionska kiselina, maslačna kiselina, benzoeva kiselina, feniloctena kiselina, cikloheksankarboksilna kiselina, kloro- ili fluoro-octena kiselina, dikloro- ili difluoro-octena kiselina, trikloro- ili trifluoro-octena kiselina, klorobenzoeva kiselina, raetansulfonska kiselina, etansulfonska kiselina, benzensulfonska kiselina, klorobenzensulfonska kiselina, trifluoro-metansulfonska kiselina, raetilfosfonska kiselina i fenilfosfonska kiselina. Kiseline kojima se daje prednost su octena kiselina, propionska kiselina, trifluorooctena kiselina, metansulfonska kiselina i klorooctena kiselina. Detaljno rečeno, postupak prema izumu može se provesti prvo dobivanjem katalizatora. Otopina nezasićenog organskog spoja doda se u otopinu katalizatora (ili vice versa) i u autoklavu se primijeni pritisak vodika, da bi se odstranio zaštitni plin koji se koristi. Reakcijska mješavina se zagrijava i po želji hidrogenira. Tamo gdje je prikladno, kad reakcija prestane, reakcijska mješavina se hladi, a pritisak u autoklavu se smanji. Reakcijska mješavina može se izbaciti iz autoklava pod pritiskom sa vodikom, a hidrogenirani organski spoj može se izolirati i pročistiti na način poznat per se, na primjer taloženjem, ekstrakcijom ili destilacijom. Potom se katalizator može ponovno kiristiti, ako je potrebno uz dodatak svježeg katalizatora, da bio se nadoknadili gubici. Examples of organic acids are aliphatic or aromatic, possibly halogenated (fluorinated or chlorinated) carboxylic acids, sulfonic acids, phosphoric (V) acids (for example phosphonic acids, phosphonic acids) with mostly from 1 to 20, especially from 1 to 12, and most often from 1 to 6 carbon atoms. Examples are formic acid, acetic acid, propionic acid, butyric acid, benzoic acid, phenylacetic acid, cyclohexanecarboxylic acid, chloro- or fluoroacetic acid, dichloro- or difluoroacetic acid, trichloro- or trifluoroacetic acid, chlorobenzoic acid, ethanesulfonic acid, ethanesulfonic acid, benzenesulfonic acid, chlorobenzenesulfonic acid, trifluoromethanesulfonic acid, raethylphosphonic acid and phenylphosphonic acid. Preferred acids are acetic acid, propionic acid, trifluoroacetic acid, methanesulfonic acid and chloroacetic acid. In detail, the process according to the invention can be carried out by first obtaining a catalyst. A solution of the unsaturated organic compound is added to the catalyst solution (or vice versa) and hydrogen pressure is applied to the autoclave to remove the shielding gas used. The reaction mixture is heated and optionally hydrogenated. Where appropriate, when the reaction has ceased, the reaction mixture is cooled and the pressure in the autoclave is reduced. The reaction mixture can be autoclaved under hydrogen pressure, and the hydrogenated organic compound can be isolated and purified in a manner known per se, for example by precipitation, extraction or distillation. Then the catalyst can be cleaned again, if necessary with the addition of fresh catalyst, to compensate for the losses.

U slučaju hidrogenizacije aldimina i ketimina, aldimini i ketimini također se mogu dobiti in situ prije ili za vrijeme hidrogenizacije. Kod preporučljivog oblika, pomiješaju se amin i aldehid ili keton i dodaju se u otopinu katalizatora i aldimiin ili ketimin dobiveni in situ se hidrogenira. No. moguće je da se amina, keton ili aldehid koriste zajedno sa katalizatorom kao početna količina, a potom se doda keton ili aldehid ili njihov amin ili najednom ili u odmjerenim količinama. Kod korištenja ove metode, dobro je da se odstrani voda reakcije koja se stvara kod formiranja imina, na primjer pomoću azeotropske destilacije ili dodavanjem sredstava koja vežu vodu. In the case of hydrogenation of aldimines and ketimines, aldimines and ketimines can also be obtained in situ before or during hydrogenation. In a preferred embodiment, the amine and aldehyde or ketone are mixed and added to the catalyst solution and the aldimine or ketimine obtained in situ is hydrogenated. But. it is possible for the amine, ketone or aldehyde to be used together with the catalyst as an initial amount, and then the ketone or aldehyde or their amine is added either all at once or in metered amounts. When using this method, it is good to remove the water of reaction that is formed during the formation of the imine, for example by azeotropic distillation or by adding water-binding agents.

Amini koji se mogu dobiti prema izumu su biološki aktivni spojevi ili intermedijati za dobivanje takovih spojeva, naročito u području dobivanja farmaceutskih ili agrokemijskih preparata. Na primjer, derivati o,o-dialkilarilketamina, naročito oni koji sadrže alkilne i/ili alkoksialkilne grupe, su učinkoviti kao fungicidi, naročito kao herbicidi. Derivati mogu biti soli amina, amidi kiselina, na primjer amidi klorooctene kiseline, tercijarni amidi i amonijeve soli (vidi na primjer, EP-A-0 077,755 i EP-A-0 115,470). Amines that can be obtained according to the invention are biologically active compounds or intermediates for obtaining such compounds, especially in the field of obtaining pharmaceutical or agrochemical preparations. For example, o,o-dialkylarylketamine derivatives, especially those containing alkyl and/or alkoxyalkyl groups, are effective as fungicides, especially as herbicides. Derivatives can be amine salts, acid amides, for example chloroacetic acid amides, tertiary amides and ammonium salts (see for example EP-A-0 077,755 and EP-A-0 115,470).

Izum se odnosi i na katalizatore hidrogenizacije koji su proizvod reakcije iridijeve(III) ili iridijeve(IV) soli ili njenih hidrata, sa difosfinom koji ima grupe sekundarnih fosfina i alkalno metalni ili amonijev klorid, bromid ili jodid. The invention also relates to hydrogenation catalysts which are the product of the reaction of iridium(III) or iridium(IV) salts or their hydrates, with diphosphine having secondary phosphine groups and alkali metal or ammonium chloride, bromide or iodide.

Izum se odnosi i na korištenje proizvoda reakcije iridijeve(III) ili iridijeve(IV) soli ili njenih hidrata kao katalizator hidrogenizacije, pri čemu difosfin ima grupe sekundarnih fosfina i alkalno metalni ili amonijev klorid, bromid ili jodid. The invention also relates to the use of the reaction product of iridium(III) or iridium(IV) salt or its hydrates as a hydrogenation catalyst, wherein the diphosphine has secondary phosphine groups and alkali metal or ammonium chloride, bromide or iodide.

Naredni primjeri detaljnije ilustriraju izum. Kemijska konverzija je određena plinskom kromatografijom (DB 17/30 W stupac (15 m), proizvođač: JCW Scientific Inc. USA, program temperature: od 60°C/1 min do 220°C, AT: 10° x min-1). Optička dobivena količina (enantiomerni suvišak, ee) određena je ili plinskom kromatografijom (Chirasil-Val stupac, 50 m, proizvođač: Alltech, USA, T=150°C, izotermička), sa HPLC (Chiracel OD stupac) ili sa 1H-NMR spektroskopijom (koristeći šift reagense). The following examples illustrate the invention in more detail. Chemical conversion was determined by gas chromatography (DB 17/30 W column (15 m), manufacturer: JCW Scientific Inc. USA, temperature program: from 60°C/1 min to 220°C, AT: 10° x min-1) . The optical amount obtained (enantiomeric excess, ee) was determined either by gas chromatography (Chirasil-Val column, 50 m, manufacturer: Alltech, USA, T=150°C, isothermal), with HPLC (Chiracel OD column) or with 1H-NMR spectroscopy (using shift reagents).

Primjeri primjene Application examples

Primjer A1: Dobivanje iridijevog katalizatora Example A1: Obtaining an iridium catalyst

9.1 mg (0.029 mmol) IrCl3 hidrata, 21.4 mg (0.033 mmol) {(R)-1-[(S)-2-difenil-fosfino)ferocenil]}etil-di(3,5-dimetilfenil) fosfina i 150 mg (0.4 mmol) tetrabutilamonijevog jodida rastvori se u 20 ml tetrahidrofurana i miješa 2 sata na 50°C. Potom se otapalo odstrani. Ostaje kruti topivi ostatak koji se kasnije koristi direktno u 9.1 mg (0.029 mmol) IrCl3 hydrate, 21.4 mg (0.033 mmol) {(R)-1-[(S)-2-diphenyl-phosphino)ferrocenyl]}ethyl-di(3,5-dimethylphenyl)phosphine and 150 mg (0.4 mmol) of tetrabutylammonium iodide is dissolved in 20 ml of tetrahydrofuran and stirred for 2 hours at 50°C. Then the solvent was removed. A solid soluble residue remains, which is later used directly in

Primjeru B1. Example B1.

Primjer B1: Dobivanje N-(2'-metil-6'-etil-fen-1'-il)-N-(1-metoksimetil)-etilamina Example B1: Preparation of N-(2'-methyl-6'-ethyl-phen-1'-yl)-N-(1-methoxymethyl)-ethylamine

Ostatak iz Primjera A1 rastvori se u 2.5 ml octene kiseline. Ta otopina katalizatora i 5 ml (0.024 mola) N-(2'-metil-6'-etil-fen-1'-il)-N-(1-metoksimetil)et-1-il-idenamina malo pomalo se prenese u čelični autoklav zapremine 50 ml, koji je pod inertnim plinom. U četiri ciklusa (10 bara, normalan pritisak), inertni plin se istisne vodikom. Potom se primijeni pritisak od 25 bara vodika. Nakon vremena reakcije od 10 satii na 25°C, reakcija se prekine. Konverzija je 100%, a optička dobivena količina je 78.8% (S). The residue from Example A1 is dissolved in 2.5 ml of acetic acid. This solution of the catalyst and 5 ml (0.024 mol) of N-(2'-methyl-6'-ethyl-phen-1'-yl)-N-(1-methoxymethyl)eth-1-yl-idenamine was transferred little by little into steel autoclave with a volume of 50 ml, which is under inert gas. In four cycles (10 bar, normal pressure), the inert gas is displaced by hydrogen. Then a pressure of 25 bar of hydrogen is applied. After a reaction time of 10 hours at 25°C, the reaction is stopped. The conversion is 100%, and the optical yield is 78.8% (S).

Primjer B2: Dobivanje N-(2'-metil-6'-etil-fen-1'-il)-N-(1-metoksimetil)etilamina Example B2: Preparation of N-(2'-methyl-6'-ethyl-phen-1'-yl)-N-(1-methoxymethyl)ethylamine

Katalizator se dobiva analogno načinu opisanom u Primjeru A1, počevši od 9.1 mg (0.029 mmol) IrCl3 hidrata, 21.4 mg (0.033 mmol) {(R)-1-[(S)-2-difenil-fosfino)ferocenil]}-etil-di(3,5-dimetilfenil)fosfina i 150 mg (0.5 mmol) tetrabutilamonijevog klorida u 20 ml THF. Katalizator se rastvori u 2.5 ml octene kiseline. Potom se provodi hidrogenizacija analogno Primjeru B1 na 60 bara vodika i 25°C. Vrijeme reakcije je 43 sata, konverzija 73%, a enantiomerni suvišak 37% (S). The catalyst is obtained analogously to the method described in Example A1, starting from 9.1 mg (0.029 mmol) of IrCl3 hydrate, 21.4 mg (0.033 mmol) of {(R)-1-[(S)-2-diphenyl-phosphino)ferrocenyl]}-ethyl -di(3,5-dimethylphenyl)phosphine and 150 mg (0.5 mmol) of tetrabutylammonium chloride in 20 ml of THF. The catalyst is dissolved in 2.5 ml of acetic acid. Hydrogenation is then carried out analogously to Example B1 at 60 bar hydrogen and 25°C. The reaction time is 43 hours, the conversion is 73%, and the enantiomeric excess is 37% (S).

Primjer B3: Dobivanje N-(2'-metil-6'-etil-fen-1'-il)-N-(1-metoksimetil)etil-amina Example B3: Preparation of N-(2'-methyl-6'-ethyl-phen-1'-yl)-N-(1-methoxymethyl)ethyl-amine

Postupak se provodi analogno Primjeru B2, no sa sljedećim izmijenjenim uvjetima reakcije: The procedure is carried out analogously to Example B2, but with the following modified reaction conditions:

150 mg (1.3 mmol) kalijevog bromida. Vrijeme reakcije je 91 sat, konverzija 100%, a enantiomerni suvišak 63% (S). 150 mg (1.3 mmol) of potassium bromide. The reaction time is 91 hours, the conversion is 100%, and the enantiomeric excess is 63% (S).

Primjer B4: Dobivanje N-(2'-metil-6'-etil-fen-1'-il)-N-(1-metoksimetil)etil-amina Example B4: Preparation of N-(2'-methyl-6'-ethyl-phen-1'-yl)-N-(1-methoxymethyl)ethyl-amine

Postupak se provodi analogno Primjeru B2, no sa sljedećim izmijenjenim uvjetima reakcije: The procedure is carried out analogously to Example B2, but with the following modified reaction conditions:

23.1 mg (0.033 mmol) {(R)-1-[(S)-2-difenilfosfino) ferocenil]}etil-di(3,5-dimetil-4-N,N-di-propilaminofenil)fosfina, 150 g (0.4 mmol) tetrabutilamonijevog jodida, 30 bara vodika. Vrijeme reakcije je 3.5 sati, konverzija 97%, a enantiomerni suvišak 81.7% (S). 23.1 mg (0.033 mmol) {(R)-1-[(S)-2-diphenylphosphino)ferrocenyl]}ethyl-di(3,5-dimethyl-4-N,N-di-propylaminophenyl)phosphine, 150 g ( 0.4 mmol) of tetrabutylammonium iodide, 30 bar of hydrogen. The reaction time is 3.5 hours, the conversion is 97%, and the enantiomeric excess is 81.7% (S).

Primjer B5: Dobivanje N-(2'-metil-6'-etil-fen-1'-il)-N-(1-metoksimetil) etil-amina Example B5: Preparation of N-(2'-methyl-6'-ethyl-phen-1'-yl)-N-(1-methoxymethyl)ethylamine

Postupak se provodi analogno Primjeru B2, no sa sljedećim izmijenjenim uvjetima reakcije: The procedure is carried out analogously to Example B2, but with the following modified reaction conditions:

14.1 mg (0.033 mmol) (2R, 4R)-bis(difenilfosfino)pentana, 150 mg (0.4 mmol) tetrabutilamonijevog jodida, vodik pod pritiskom od 30 bara. Vrijeme reakcije je 21.5 sati,, konverzija 95%, a enantiomerni suvišak 46.9 % (S). 14.1 mg (0.033 mmol) (2R, 4R)-bis(diphenylphosphino)pentane, 150 mg (0.4 mmol) tetrabutylammonium iodide, hydrogen under a pressure of 30 bar. The reaction time is 21.5 hours, the conversion is 95%, and the enantiomeric excess is 46.9% (S).

Primjer B6: Dobivanje N-(2'-metil-6'-etil-fen-1'-ill)-N-(l1-metoksimetil) etil-amina Example B6: Preparation of N-(2'-methyl-6'-ethyl-phen-1'-yl)-N-(11-methoxymethyl)ethylamine

Postupak se provodi analogno Primjeru B2, no sa sljedećim izmijenjenim uvjetima reakcije: The procedure is carried out analogously to Example B2, but with the following modified reaction conditions:

15.4 mg (0.029 mmol) IrBr3 hidrata, 19.5 mg (0.033 mmol) {(R)-1-[(S)-di-(2-metilfenil)fosfino)ferocenil]}etil-difenilfosfina, 0.1 ml trifluorooctene kiseline u 5 ml toluena, 150 mg (0.4 mmol) tetrabutilamonijevog jodida. Vrijeme reakcije je 71 sat, konverzija 15%, a enantiomerni suvišak 29.4 % (S). 15.4 mg (0.029 mmol) IrBr3 hydrate, 19.5 mg (0.033 mmol) {(R)-1-[(S)-di-(2-methylphenyl)phosphino)ferrocenyl]}ethyl-diphenylphosphine, 0.1 ml trifluoroacetic acid in 5 ml toluene, 150 mg (0.4 mmol) tetrabutylammonium iodide. The reaction time is 71 hours, the conversion is 15%, and the enantiomeric excess is 29.4% (S).

Primjer B7: Dobivanje N-(2'-metil-6'-etil-fen-1'-il)-N-(1-metoksimetil) etil-amina Example B7: Preparation of N-(2'-methyl-6'-ethyl-phen-1'-yl)-N-(1-methoxymethyl)ethylamine

Postupak se provodi analogno Primjeru B2, no sa sljedećim izmijenjenim uvjetima reakcije: The procedure is carried out analogously to Example B2, but with the following modified reaction conditions:

19.9 mg (0.033 mmol) (R)(+)-2,2'-bis(difenilfosfino)-1,1'-binaftalena, 0.1 ml metansulfonske kiseline u 2.5 ml toluena i 2 ml izopropanola, 150 mg (0.4 mmol) tetrabutilamonijevog jodida, vodik pod pritiskom od 30 bara. Vrijeme reakcije je 56 sati, konverzija 75%, a enantiomerni suvišak 31%. 19.9 mg (0.033 mmol) (R)(+)-2,2'-bis(diphenylphosphino)-1,1'-binaphthalene, 0.1 ml of methanesulfonic acid in 2.5 ml of toluene and 2 ml of isopropanol, 150 mg (0.4 mmol) of tetrabutylammonium of iodide, hydrogen under a pressure of 30 bar. The reaction time is 56 hours, the conversion is 75%, and the enantiomeric excess is 31%.

Primjer B8: Dobivanje N-(2'-metil-6'-etil-fen-1'-il)-N-(1-metoksimetil) etil-amina Example B8: Preparation of N-(2'-methyl-6'-ethyl-phen-1'-yl)-N-(1-methoxymethyl)ethylamine

Katalizator se dobiva analogno načinu opisanom u Primjeru A1, počevši od 9.1 mg (0.029 mmol) IrCl3 hidrata, 15.6 mg (0.033 mmol) (4S,5S)-(+)-4,5-bis(difenilfosfinometil)-2,2-dimetil-1,3-dioksalana i 150 mg (0.4 mmol) tetrabutilamonijevog jodida u 20 ml THF. Katalizator se rastvori u 5 ml izopropanola. Potom se hidrogenizacija provodi analogno Primjeru B1 na 30 bara vodika i 25°C. Vrijeme reakcije je 22 sata, konverzija 21 %. The catalyst is obtained analogously to the method described in Example A1, starting from 9.1 mg (0.029 mmol) of IrCl3 hydrate, 15.6 mg (0.033 mmol) of (4S,5S)-(+)-4,5-bis(diphenylphosphinomethyl)-2,2- dimethyl-1,3-dioxalane and 150 mg (0.4 mmol) of tetrabutylammonium iodide in 20 ml of THF. The catalyst is dissolved in 5 ml of isopropanol. Hydrogenation is then carried out analogously to Example B1 at 30 bar hydrogen and 25°C. Reaction time is 22 hours, conversion 21%.

Primjer B9: Dobivanje N-(2'-metil-6'-etil-fen-1'-il)-N-(1-metoksimetil) etil-amina Example B9: Preparation of N-(2'-methyl-6'-ethyl-phen-1'-yl)-N-(1-methoxymethyl)ethylamine

5 ml (0.024 mmol) N-(2'-metil-6'-etil-fen-1'-il)-N-(1-metoksi-metil) etilidenamina, 2 ml octene kiseline, 14.6 mg (0.03 mmol) H2IrCl6⋅6H2O, 21.4 mg (0.033 mmol) {(R)-1-[(S)-2-difenilfosfino) ferocenil]}etil-di(3,5-di-metilfenil)fosfina i 150 mg (0.5 mmol) tetrabutilamonijevog klorida se jedno po jedno prenese u čelični autoklav zapremine 50 ml. Autoklav se potom zatvori i stavi pod argonsku atmosferu. Na kraju se plinski površinski sloj izmijeni i primijeni se pritisak od 25 bara vodika. Nakon vremena reakcije od 18 sati na sobnoj temperaturi, dobiva se konverzija od 92 % i ee od 76.6 % (S). 5 ml (0.024 mmol) N-(2'-methyl-6'-ethyl-phen-1'-yl)-N-(1-methoxy-methyl) ethylideneamine, 2 ml acetic acid, 14.6 mg (0.03 mmol) H2IrCl6 ⋅6H2O, 21.4 mg (0.033 mmol) {(R)-1-[(S)-2-diphenylphosphino)ferrocenyl]}ethyl-di(3,5-di-methylphenyl)phosphine and 150 mg (0.5 mmol) tetrabutylammonium chloride are transferred one by one to a steel autoclave with a volume of 50 ml. The autoclave is then closed and placed under an argon atmosphere. Finally, the gas surface layer is changed and a pressure of 25 bar hydrogen is applied. After a reaction time of 18 hours at room temperature, a conversion of 92% and an ee of 76.6% (S) are obtained.

Claims (48)

1. Iridijev spoj koji se dobiva reakcijom soli iridija(III) ili iridija(IV) ili njenog hidrata i difosfina, naznačen time, što ima grupe sekundarnog fosfina u prisustvu metalnog ili amonijevog klorida, bromida ili jodida.1. An iridium compound obtained by the reaction of an iridium(III) or iridium(IV) salt or its hydrate and diphosphine, indicated by the fact that it has secondary phosphine groups in the presence of metal or ammonium chloride, bromide or iodide. 2. Iridijev spoj prema zahtjevu 1, naznačen time, što je sol iridija(III) ili njenog hidrata formule I [image] u kojem je X n-valentan anion jedne kiseline, n je 1, 2 ili 3, a m je 0 ili cijeli broj fakcije veće od 0 i do 8.2. Iridium compound according to claim 1, characterized in that it is a salt of iridium(III) or its hydrate of formula I [image] in which X is the n-valent anion of one acid, n is 1, 2 or 3, a m is 0 or an integer fraction greater than 0 and up to 8. 3. Iridijev spoj prema zahtjevu 2, u kojem je je XnӨ anion organske kiseline iz grupe alifatskih ili aromatskih karboksilnih kiselina, sulfonskih kiselina i fosfonskih kiselina, naznačen time, što sadrže od 1 do 12 atoma ugljika koji su nesupstituirani ili supstituirani sa F ili Cl; ili anion anorganske kiseline iz sljedeće grupe: halogenvodikove (hydrohalic) kiseline, tetrafluorborna kiselina, tetrafenilborna kiselina, heksafluoro-fosforna, -arsenova, antimonova i -bizmutska kiselina, oksi-kiseline elemenata N, P, S, F, Cl, Br i I.3. The iridium compound according to claim 2, in which XnШ is an anion of an organic acid from the group of aliphatic or aromatic carboxylic acids, sulfonic acids and phosphonic acids, indicated by the fact that they contain from 1 to 12 carbon atoms that are unsubstituted or substituted with F or Cl ; or anion of an inorganic acid from the following group: hydrohalic acid, tetrafluoroboric acid, tetraphenylboric acid, hexafluorophosphoric, -arsenic, antimony and -bismuth acids, oxy-acids of the elements N, P, S, F, Cl, Br and I . 4. Iridijev spoj prema zahtjevu 2, naznačen time, što je XnӨ halid.4. Iridium compound according to claim 2, characterized in that XnШ is a halide. 5. Iridijev spoj prema zahtjevu 2, naznačen time, što je sol iridija(III) formule I IrCl3⋅H2O, gdje je m broj od 1 do 4.5. The iridium compound according to claim 2, characterized in that it is an iridium(III) salt of the formula I IrCl3⋅H2O, where m is a number from 1 to 4. 6. Iridijev spoj prema zahtjevu 1, naznačen time, što je metalni kation ili kation alkalnog metala u halidu metala ili alkalnog metala Li⊕, Na⊕ i K⊕.6. The iridium compound according to claim 1, characterized in that the metal cation or alkali metal cation in the metal or alkali metal halide is Li⊕, Na⊕ and K⊕. 7. Iridijev spoj prema zahtjevu 1, naznačen time, što je kation amonija u amonijevom halidu NH4⊕, primarni amonij sa 1 do 20 atoma ugljika, sekundarni amonij sa 2 do 24 atoma ugljika, tercijarni amonij sa 3 do 24 atoma ugljika ili kvarternarni amonij sa 4 do 24 atoma ugljika.7. The iridium compound according to claim 1, characterized in that the ammonium cation in the ammonium halide is NH4⊕, primary ammonium with 1 to 20 carbon atoms, secondary ammonium with 2 to 24 carbon atoms, tertiary ammonium with 3 to 24 carbon atoms or quaternary ammonium with 4 to 24 carbon atoms. 8. Iridijev spoj prema zahtjevu 7, naznačen time, što je katjon kvarternarnog amonija u amonijevom halidu kation kvarternarnog amonija formule fenilN⊕-(C1-C6alkil)3, benzilN⊕(C1-C6)alkil3 ili (C1-C6alkil)4N⊕.8. The iridium compound according to claim 7, characterized in that the quaternary ammonium cation in the ammonium halide is a quaternary ammonium cation of the formula phenylN⊕-(C1-C6alkyl)3, benzylN⊕(C1-C6)alkyl3 or (C1-C6alkyl)4N⊕. 9. Iridijev spoj prema zahtjevu 1, naznačen time, što je halid alkalnog metala ili amonijev halid bromid ili jodid.9. The iridium compound according to claim 1, characterized in that the alkali metal halide or ammonium halide is bromide or iodide. 10. Iridijev spoj prema zahtjevu 9, naznačen time, što je halid alkalnog metala ili amonijev halid Lil, Nal ili Kl ili )C1-C6)NI.10. The iridium compound according to claim 9, characterized in that the alkali metal halide or ammonium halide is Li1, Na1 or K1 or (C1-C6)NI. 11. Iridijev spoj prema zahtjevu 9, naznačen time, što je amonijev halid tetrabutilamonijev jodid.11. The iridium compound according to claim 9, characterized in that the ammonium halide is tetrabutylammonium iodide. 12. Iridijev spoj prema zahtjevu 1, naznačen time, što je difosfin sa grupama sekundarnog fosfina uglavnom difosfin (a) čije fosfinske grupe su vezane na različite atome ugljika ili lanac ugljika sa 2 do 4 atoma ugljika ili (b) čije fosfinske grupe su vezane ili direktno ili preko mosne grupe -CRaRb- u orto pozicijama ciklopentadienilnog prstena ili je svaka vezana na ciklopentadienilni prsten ferocenila ili (c) čija je jedna fosfinska grupa vezana na lanac ugljika sa 2 ili 3 atoma ugljika, a druga fosfinska grupa je vezana na atom kisika ili atom dušika, koji je završno vezan na taj lanac ugljika ili (d) čije fosfinske grupe su vezane na dva atoma kisika ili atome dušika, završno vezane na C2-lanac ugljika; sa rezultatom, da je u slučajevima (a), (b), (c) i (d) prsten sa 5, 6 ili 7 članova formiran zajedno sa Ir atomom, a Ra i Rb, su neovisno jedan od drugoga vodik, C1-C8alkil, C1-C4fluoroalkil, fenil ili benzil ili su fenil ili benzil sa 1 do 3 supstituenta C1-C4alkila ili C1-C4alkoksila.12. Iridium compound according to claim 1, characterized in that diphosphine with secondary phosphine groups is mainly diphosphine (a) whose phosphine groups are attached to different carbon atoms or a carbon chain with 2 to 4 carbon atoms or (b) whose phosphine groups are attached either directly or via a bridging group -CRaRb- in the ortho positions of the cyclopentadienyl ring or each is attached to the cyclopentadienyl ring of ferrocenyl or (c) whose one phosphine group is attached to a carbon chain with 2 or 3 carbon atoms, and the other phosphine group is attached to an oxygen atom or a nitrogen atom, which is terminally attached to that carbon chain, or (d) whose phosphine groups are attached to two oxygen atoms or nitrogen atoms, terminally attached to the C2 carbon chain; with the result that in cases (a), (b), (c) and (d) a ring with 5, 6 or 7 members was formed together with an Ir atom, and Ra and Rb, independently of each other, are hydrogen, C1- C8alkyl, C1-C4fluoroalkyl, phenyl or benzyl or is phenyl or benzyl with 1 to 3 C1-C4alkyl or C1-C4alkyl substituents. 13. Iridijev spoj prema zahtjevu 1, naznačen time, što difosfin sadrži najmanje jedan kiralni atom ugljika.13. The iridium compound according to claim 1, characterized in that the diphosphine contains at least one chiral carbon atom. 14. Iridijev spoj prema zahtjevu 1, naznačen time, što grupe sekundarnih difosfina sadrže dva identična ili različita radikala od sljedeće grupe: linearni ili razgranati C1-C12alkil; nesupstituirani ili C1-C6alkilom ili C1-C6alkoksilom supstituirani C5-C12cikloalkil-CH2-, fenil ili benzil, te fenil ili benzil supstituiran sa halogenom (napr. F, Cl ili Br), C1-C6haloalkilom, (C1-C12alkil)3Si, (C6H5)3Si, C1-C6haloalkoksilom (napr. trifluorometoksil), -NH2, fenil2N-, benzil2N-, morfolinilom, piperidinilom, pirolidinilom, (C1-C12alkil)2N-, -amonij-XnӨ, -SO3M1, -CO2M1, -PO3M1 ili sa -COO-C1-C6alkilom, gdje je M1 alkalni metal ili vodik, a XnӨ je anion monobazične kiseline.14. Iridium compound according to claim 1, characterized in that the secondary diphosphine groups contain two identical or different radicals from the following group: linear or branched C1-C12 alkyl; unsubstituted or C1-C6alkyl or C1-C6alkyl-substituted C5-C12cycloalkyl-CH2-, phenyl or benzyl, and phenyl or benzyl substituted with halogen (e.g. F, Cl or Br), C1-C6haloalkyl, (C1-C12alkyl)3Si, ( C6H5)3Si, C1-C6haloalkyl (e.g. trifluoromethoxy), -NH2, phenyl2N-, benzyl2N-, morpholinyl, piperidinyl, pyrrolidinyl, (C1-C12alkyl)2N-, -ammonium-XnШ, -SO3M1, -CO2M1, -PO3M1 or with -COO-C1-C6alkyl, where M1 is an alkali metal or hydrogen and XnШ is an anion of a monobasic acid. 15. Iridijev spoj prema zahtjevu 1, naznačen time, što je difosfin formule: [image] [image] ili [image] u kojoj su; R15 i R16 neovisno jedan od drugoga vodik, C1-C4 alkil, fenil, benzil ili fenil ili benzil sa 1 do 3 C1-C4 alkil ili C1-C4 alkoksi supstituenta, R14 je vodik, C1-C4 alkil, fenil, benzil ili fenil ili benzil sa 1 do 3 C1-C4 alkil ili C1-C4 alkoksi supstituenta, R17 je vodik, C1-C4alkil, fenil, benzil, C1-C6alkoksi-CO-, C1-C6alkil-CO, fenil-CO-, naftil-CO- ili C1-C4alkilNH-CO-, A je difosfinska grupa -PR2, u kojoj je R C1-C6alkil, cikloheksil, fenil, benzil ili fenil ili bezil sa 1 do 3 C1-C4alkil, C1-C4alkoksi, -CF3 ili djelomično ili u potpunosti fluorinirana C1-C4 alkoksi supstituenta, a n je 0, 1 ili 2.15. The iridium compound according to claim 1, characterized in that it is a diphosphine of the formula: [image] [image] or [image] in which they are; R15 and R16 are independently hydrogen, C1-C4 alkyl, phenyl, benzyl or phenyl or benzyl with 1 to 3 C1-C4 alkyl or C1-C4 alkoxy substituents, R14 is hydrogen, C1-C4 alkyl, phenyl, benzyl or phenyl or benzyl with 1 to 3 C1-C4 alkyl or C1-C4 alkoxy substituents, R17 is hydrogen, C1-C4alkyl, phenyl, benzyl, C1-C6 alkoxy-CO-, C1-C6alkyl-CO, phenyl-CO-, naphthyl-CO- or C1-C4alkylNH-CO-, A is a diphosphine group -PR2, in which R is C1-C6alkyl, cyclohexyl, phenyl, benzyl or phenyl or bezil with 1 to 3 C1-C4alkyl, C1-C4alkoxy, -CF3 or partially or fully fluorinated C1-C4 alkoxy substituents, and n is 0, 1 or 2. 16. Iridijev spoj prema zahtjevu 15, naznačen time, što je difosfin {(R)-1-[(S)-2-difenilfosfino)ferocenil]}etil-di(3,5-dimetil-4-N,N-dipropil-aminofenil)fosfin {(R)-1-[(S)-2-difenilfosfino)ferocenil]}etil-di(3,5-diiizopropil-4-N,N-dimetil-aminofenil)fosfin {(R)-1-[(S)-2-difenilfosfino)ferocenil]}etil-di(3,5-diizopropil-4-N,N-dibenzilil-aminofenil)fosfin {(R)-1-[(S)-2-difenilfosfino)ferocenil]}etil-di(3,5-dimetil-4-N,N,-dibenzilil-aminofenil)fosfin {(R)-1-[(S)-2-difenilfosfino)ferocenil]}etil-di(3,5-dimetil-4-(1'-pirolo)-fenil)fosfin {(R)-1-[(S)-2-difenilfosfino)ferocenil]}etil-di(3,5-dimetil-4-N,N-dipentil-aminofenil)fosfin {(R)-1-[(S)-2-difenilfosfino)ferocenil]}etil-di(3,5-dimetil-4-N,N-dimetil-aminofenil)fosfin 1,4-bis(difenilfosfino)butan {(R)-1-[(S)-2-di(4-metoksifenil)fosfino)ferocenil]}etil-di(3,5-dimetil-4-N,N-dimetilaminofenil)fosfin, a naročito {(R)-1-[(S)-2-difenilfosfino)ferocenil]}etil-di(3,5-dimetil-fenil)fosfin.16. Iridium compound according to claim 15, characterized in that it is diphosphine {(R)-1-[(S)-2-diphenylphosphino)ferrocenyl]}ethyl-di(3,5-dimethyl-4-N,N-dipropyl-aminophenyl)phosphine {(R)-1-[(S)-2-diphenylphosphino)ferrocenyl]}ethyl-di(3,5-diisopropyl-4-N,N-dimethyl-aminophenyl)phosphine {(R)-1-[(S)-2-diphenylphosphino)ferrocenyl]}ethyl-di(3,5-diisopropyl-4-N,N-dibenzylyl-aminophenyl)phosphine {(R)-1-[(S)-2-diphenylphosphino)ferrocenyl]}ethyl-di(3,5-dimethyl-4-N,N,-dibenzylyl-aminophenyl)phosphine {(R)-1-[(S)-2-diphenylphosphino)ferrocenyl]}ethyl-di(3,5-dimethyl-4-(1'-pyrrolo)-phenyl)phosphine {(R)-1-[(S)-2-diphenylphosphino)ferrocenyl]}ethyl-di(3,5-dimethyl-4-N,N-dipentyl-aminophenyl)phosphine {(R)-1-[(S)-2-diphenylphosphino)ferrocenyl]}ethyl-di(3,5-dimethyl-4-N,N-dimethyl-aminophenyl)phosphine 1,4-bis(diphenylphosphino)butane {(R)-1-[(S)-2-di(4-methoxyphenyl)phosphino)ferrocenyl]}ethyl-di(3,5-dimethyl-4-N,N-dimethylaminophenyl)phosphine, and especially {(R)-1-[(S)-2-diphenylphosphino)ferrocenyl]}ethyl-di(3,5-dimethyl-phenyl)phosphine. 17. Postupak za dobivanje iridijevog spoja, naznačen time, što sadrži reakciju sa drugim, barem ekvimolarnim količinama soli iridija (III) ili iridija(IV) ili njenih hidrata i difosfinom koja ima grupe sekundarnih fosfina u prisustvu alkalno metalnog ili amonijevog klorida, bromida ili jodida.17. Process for obtaining an iridium compound, indicated by the fact that it contains a reaction with other, at least equimolar amounts of iridium (III) or iridium (IV) salts or their hydrates and diphosphine having secondary phosphine groups in the presence of alkali metal or ammonium chloride, bromide or iodide. 18. Postupak prema zahtjevu 17, naznačen time, što je moarni odnos soli iridija(III) ili iridija(IV) ili njenog hidrata prema difosfinu 1:1 do 1:1.5.18. The method according to claim 17, characterized in that the molar ratio of the salt of iridium(III) or iridium(IV) or its hydrate to diphosphine is 1:1 to 1:1.5. 19. Postupak prema zahtjevu 17, naznačen time, što se alkalno metalni ili amonijev klorid, bromid ili jodid koriste u suvišku, temeljeno na soli iridija(III) ili iridija(IV) ili njenog hidrata.19. The method according to claim 17, indicated by the fact that alkali metal or ammonium chloride, bromide or iodide is used in excess, based on the salt of iridium(III) or iridium(IV) or its hydrate. 20. Postupak prema zahtjevu 17, naznačen time, što je temperatura reakcije od -20°C do 100°C.20. The method according to claim 17, characterized in that the reaction temperature is from -20°C to 100°C. 21. Postupak prema zahtjevu 17, naznačen time, što se reakcija provodi u dipolarnom otapalu.21. The method according to claim 17, characterized in that the reaction is carried out in a dipolar solvent. 22. Postupak prema zahtjevu 17, naznačen time, što je difosfin: {(R)-1-[(S)-2-difenilfosfino)ferocenil]}etil-di(3,5-dimetil-4-N,N-dipropil-aminofenil)fosfin {(R)-1-[(S)-2-difenilfosfino)ferocenil]}etil-di(3,5-diiizopropil-4-N,N-dimetil-aminofenil)fosfin {(R)-1-[(S)-2-difenilfosfino)ferocenil]}etil-di(3,5-diizopropil-4-N,N-dibenzilil-aminofenil)fosfin {(R)-1-[(S)-2-difenilfosfino)ferocenil]}etil-di(3,5-dimetil-4-N,N,-dibenzilil-aminofenil)fosfin {(R)-1-[(S)-2-difenilfosfino)ferocenil]}etil-di(3,5-dimetil-4-(1'-pirolo)-fenil)fosfin {(R)-1-[(S)-2-difenilfosfino)ferocenil]}etil-di(3,5-dimetil-4-N,N-dipentil-aminofenil)fosfin {(R)-1-[(S)-2-difenilfosfino)ferocenil]}etil-di(3,5-dimetil-4-N,N-dimetil-aminofenil)fosfin 1,4-bis(difenilfosfino)butan {(R)-1-[(S)-2-di(4-metoksifenil)fosfino)ferocenil]}etil-di(3,5-dimetil-4-N,N-dimetilaminofenil)fosfin, a naročito {(R)-1-[(S)-2-difenilfosfino)ferocenil]}etil-di(3,5-dimetil-fenil)fosfin.22. The method according to claim 17, characterized in that the diphosphine is: {(R)-1-[(S)-2-diphenylphosphino)ferrocenyl]}ethyl-di(3,5-dimethyl-4-N,N-dipropyl-aminophenyl)phosphine {(R)-1-[(S)-2-diphenylphosphino)ferrocenyl]}ethyl-di(3,5-diisopropyl-4-N,N-dimethyl-aminophenyl)phosphine {(R)-1-[(S)-2-diphenylphosphino)ferrocenyl]}ethyl-di(3,5-diisopropyl-4-N,N-dibenzylyl-aminophenyl)phosphine {(R)-1-[(S)-2-diphenylphosphino)ferrocenyl]}ethyl-di(3,5-dimethyl-4-N,N,-dibenzylyl-aminophenyl)phosphine {(R)-1-[(S)-2-diphenylphosphino)ferrocenyl]}ethyl-di(3,5-dimethyl-4-(1'-pyrrolo)-phenyl)phosphine {(R)-1-[(S)-2-diphenylphosphino)ferrocenyl]}ethyl-di(3,5-dimethyl-4-N,N-dipentyl-aminophenyl)phosphine {(R)-1-[(S)-2-diphenylphosphino)ferrocenyl]}ethyl-di(3,5-dimethyl-4-N,N-dimethyl-aminophenyl)phosphine 1,4-bis(diphenylphosphino)butane {(R)-1-[(S)-2-di(4-methoxyphenyl)phosphino)ferrocenyl]}ethyl-di(3,5-dimethyl-4-N,N-dimethylaminophenyl)phosphine, and especially {(R)-1-[(S)-2-diphenylphosphino)ferrocenyl]}ethyl-di(3,5-dimethyl-phenyl)phosphine. 23. Postupak za katalitičku hidrogenizaciju imina sa vodikom pod povišenim pritiskom u prisustvu iridijevog katalizatora i sa ili bez inertnog otapala, naznačen time, što se kao katalizator koristi iridijev spoj prema zahtjevu 1.23. Process for the catalytic hydrogenation of imines with hydrogen under elevated pressure in the presence of an iridium catalyst and with or without an inert solvent, characterized in that the iridium compound according to claim 1 is used as a catalyst. 24. Postupak prema zahtjevu 23, naznačen time, što imin sadrži najmanje jednu [image] 24. The method according to claim 23, characterized in that the imine contains at least one [image] 25. Postupak prema zahtjevu 23, naznačen time, što imin sadrži najmanje jednu od grupa [image] i dodatno nezasićene grupe [image] 25. The method according to claim 23, characterized in that the imine contains at least one of the groups [image] and additionally unsaturated groups [image] 26. Postupak prema zahtjevu 25, naznačen time, što su slobodne veze zasićene sa vodikom ili organskim radikalima koji imaju od 1 do 22 atoma ugljika ili organskim heteroradikalima koji imaju od 1 do 20 atoma ugljika i najmanje jedan heteroatom iz grupe 0, S, N i P; ili je atom dušika grupe [image] zasićen sa NH2 ili sa primarnom amino grupom koja ima od 1 do 22 atoma ugljika ili sa sekundarnom amino grupom koja ima 2 do 40 atoma ugljika.26. The method according to claim 25, characterized in that the free bonds are saturated with hydrogen or organic radicals having from 1 to 22 carbon atoms or organic heteroradicals having from 1 to 20 carbon atoms and at least one heteroatom from the group 0, S, N and P; or is the nitrogen atom of the group [image] saturated with NH2 or with a primary amino group having from 1 to 22 carbon atoms or with a secondary amino group having from 2 to 40 carbon atoms. 27. Postupak prema zahtjevu 23, naznačen time, što su aldimini, ketimini i hidrazoni hidrogenirani.27. Process according to claim 23, characterized in that aldimines, ketimines and hydrazones are hydrogenated. 28. Postupak prema zahtjevu 27, naznačen time, što je imin formule III [image] koji je hidrogeniran da bi se dobio amin formule IV [image] u kojoj je R3 uglavnom supstituent i u kojoj je R3 linearni ili razgranati C1-C12alkil, cikloalkil koji ima od 3 do 8 atoma ugljika; heterocikloalkil vezan preko atoma ugljika, sa 3 do 8 prstenastih atoma i 1 ili 2 heteroatoma iz grupe O, S i NR6; C7-C16aralkil vezan preko atoma alkilugljika ili C1-C12alkil supstituiran sa spomenutim cikloalkilom ili heterocikloalkilom ili heteroarilom; ili gdje je R3 C1-C12aril ili C4-C11heteroaril vezan preko prstenastog atoma ugljika i koji ima 1 ili 2 heteroatoma u prstenu; R3 je nesupstituiran ili supstituiran sa -CN, -NO2, F, Cl, C1-C12alkilom, C1-C12alkoksilom, C1-C12alkiltio, C1-C6haloalkilom, -OH, C6-C12arilom ili -ariloksilom ili -ariltio, C7-C16aralkilom ili -aralkoksilom ili -aralkiltio, sekundarnim aminom koji ima od 2 do 24 atoma ugljika, -CONR4R5 ili sa -COOR4, a radikali arila i arilne grupe u aralkilu, aralkoksilu i aralkiltio su nesupstituirane iuli supstituirane sa -CN, -NO2, F, Cl, C1-C4-alkilom, -alkoksilom ili -alkiltio, -OH, CONR4R5 ilj sa -COOR4; R4 i R5 su neovisno jedan od drugoga vodik, C1-C12alkil, fenil ili benzil ili su R4 i R5 zajedno tetra- ili penta-metilen ili 3-oksapentilen; R6 ima isto značenje kao R4; R1 i R2 su neovisno jedan od drugoga atom vodika, C1-C12alkil ili cikloalkil sa 3 do 8 prstenastih atoma ugljika, od kojih je svaki nesupstituiran ili supstituiran sa -OH, C1-C12alkoksilom, fenoksilom, benziloksilom, sekundarnim aminom koji ima od 2 do 24 atoma ugljika, -CONR4R5 ili sa -COOR4; C6-C12aril ili C7-C16aralkil koji je nesupstituiran ili supstituiran ka R3 ili -CONR4R5, gdje su R4 i R5 kao što je gore definirano; ili R3 je definiran kao gore, a R1 i R2 zajedno su alkilen koji ima 2 do 5 atoma ugljika koji su eventualno prekinuti sa 1 ili 2 -O-, -S- ili NRg radikalima i/ili nesupstituriani ili supstituirani sa =0 ili kao R1 i R2 gore u značenju alkila i/ili kondenzirani sa benzenom, piridinom, pirimidinom, furanom, tiofenom ili pirolom; ili R2 je definiran kao gore, a R1 i R3 su zajedno alkilen koji ima od 2 do 5 atoma ugljika, koji je eventualno prekinut sa 1 ili 2 -0-, -S- ili -NR6-radikala i/ili nesupstituiran ili supstituiran sa =0 ili kao R1 i R2 gore u značenju alkila i/ili kondenziran sa benzenom, piridinom, pirimidinom, furanom, tiofenom ili pirolom.28. The method according to claim 27, characterized in that the imine of formula III [image] which is hydrogenated to give an amine of formula IV [image] in which it is R3 is mostly a substituent and in which it is R 3 linear or branched C 1 -C 12 alkyl, cycloalkyl having from 3 to 8 carbon atoms; heterocycloalkyl linked through a carbon atom, with 3 to 8 ring atoms and 1 or 2 heteroatoms from the group O, S and NR6; C7-C16aralkyl attached via an alkylcarbon atom or C1-C12alkyl substituted with said cycloalkyl or heterocycloalkyl or heteroaryl; or where it is R3 C1-C12aryl or C4-C11heteroaryl bonded through a ring carbon atom and having 1 or 2 heteroatoms in the ring; R 3 is unsubstituted or substituted with -CN, -NO 2 , F, Cl, C 1 -C 12 alkyl, C 1 -C 12 alkoxy, C 1 -C 12 alkylthio, C 1 -C 6 haloalkyl, -OH, C 6 -C 12 aryl or -aryloxy or -arylthio, C 7 -C 16 aralkyl or - with aralkyl or -aralkylthio, secondary amine having from 2 to 24 carbon atoms, -CONR4R5 or with -COOR4, and aryl radicals and aryl groups in aralkyl, aralkyl and aralkylthio are unsubstituted or substituted with -CN, -NO2, F, Cl, by C1-C4-alkyl, -alkyloxy or -alkylthio, -OH, CONR4R5 or with -COOR4; R4 and R5 are independently hydrogen, C1-C12alkyl, phenyl or benzyl or are R4 and R5 together are tetra- or penta-methylene or 3-oxapentylene; R 6 has the same meaning as R 4 ; R1 and R2 are, independently of each other, a hydrogen atom, C1-C12alkyl or cycloalkyl with 3 to 8 ring carbon atoms, each of which is unsubstituted or substituted with -OH, C1-C12alkyl, phenoxyl, benzyloxyl, a secondary amine having from 2 to 24 carbon atoms, -CONR4R5 or with -COOR4; C 6 -C 12 aryl or C 7 -C 16 aralkyl which is unsubstituted or substituted by R 3 or -CONR 4 R 5 , where R 4 and R 5 are as defined above; or R3 is defined as above, and R1 and R2 together are alkylene having 2 to 5 carbon atoms optionally terminated by 1 or 2 -O-, -S- or NRg radicals and/or unsubstituted or substituted with =0 or as R1 and R 2 above in the meaning of alkyl and/or fused with benzene, pyridine, pyrimidine, furan, thiophene or pyrrole; or R2 is defined as above, and R1 and R3 together are alkylene having from 2 to 5 carbon atoms, which is optionally terminated by 1 or 2 -O-, -S- or -NR6-radicals and/or unsubstituted or substituted with = 0 or as R1 and R2 above in the meaning of alkyl and/or condensed with benzene, pyridine, pyrimidine, furan, thiophene or pyrrole. 29. Postupak prema zahtjevu 27, naznačen time, što R1 i R2 kao heteroaril formiraju prsten sa 5 ili 6 članova, koji ima 1 ili 2 identična ili različita heteroatoma.29. The method according to claim 27, characterized in that R1 and R2 as heteroaryl form a ring with 5 or 6 members, which has 1 or 2 identical or different heteroatoms. 30. Postupak prema zahtjevu 27, naznačen time, što su R1 i R2 kao heteroarilom-supstituirani alkil, izvedeni iz prstena sa ili 6 članova koji ima 1 ili 2 identična ili različita heteroatoma.30. The method according to claim 27, characterized in that R1 and R2 are heteroaryl-substituted alkyl, derived from a ring with or 6 members having 1 or 2 identical or different heteroatoms. 31. Postupak prema zahtjevu 27, naznačen time, što R1 i R2 kao heterocikloalkil ili kao heterocikloalkilom-supstituirani alkil, sadrže od 4 do 6 prstenastih atoma i 1 ili 2 identična ili različita heteroatoma iz grupe O, S i NR5, gdje je R5 vodik, C1-C12 alkil, fenil ili benzil.31. The method according to claim 27, characterized in that R1 and R2 as heterocycloalkyl or as heterocycloalkyl-substituted alkyl contain from 4 to 6 ring atoms and 1 or 2 identical or different heteroatoms from the group O, S and NR5, where R5 is hydrogen , C1-C12 alkyl, phenyl or benzyl. 32. Postupak prema zahtjevu 27, naznačen time, što su R1 i R2i R3 kao alkil nesupstituirani ili supstituirani C1-C6alkil.32. The method according to claim 27, characterized in that R1 and R2 and R3 are unsubstituted alkyl or substituted C1-C6 alkyl. 33. Postupak prema zahtjevu 27, naznačen time, što R1 i R2i R3 kao nesupstituirani ili supstituirani cikloalkil sadrže od 3 do 6 prstenastih atoma ugljika.33. The method according to claim 27, characterized in that R1 and R2 and R3 as unsubstituted or substituted cycloalkyl contain from 3 to 6 ring carbon atoms. 34. Postupak prema zahtjevu 27, naznačen time, što su R1 i R2i R3 kao aril nesupstituirani ili supstituirani naftil ili fenil, a R1 i R2i R3 kao aralkil su nesupstituirani ili supstituirani fenilalkil sa 1 do 10 atoma ugljika u alkilenu.34. The method according to claim 27, characterized in that R1 and R2 and R3 as aryl are unsubstituted or substituted naphthyl or phenyl, and R1 and R2 and R3 as aralkyl are unsubstituted or substituted phenylalkyl with 1 to 10 carbon atoms in alkylene. 35. Postupak prema zahtjevu 27, naznačen time, R1 i R2 zajedno ili R1 i R3 zajedno čine sa atomom ugljika ili -N = C grupom na koju su vezani, prsten sa 5 ili 6 članova.35. The method according to claim 27, characterized in that R1 and R2 together or R1 and R3 together form a ring with 5 or 6 members with the carbon atom or -N = C group to which they are attached. 36. Postupak prema zahtjevu 27, naznačen time, što u formuli I R3 je 2,6-di-C1-C4alkilfen-1-il, Ri je C1-C4alkil, a R2 je C1-C4alkil, C1-C4alkoksietil.36. The method according to claim 27, characterized in that in formula I R3 is 2,6-di-C1-C4alkylphen-1-yl, R1 is C1-C4alkyl, and R2 is C1-C4alkyl, C1-C4alkoxyethyl. 37. Postupak prema zahtjevu 36, naznačen time, što je R3 2,6-dimetilfen-1-il ili 2-metil-6-etilfen-1-il, R1 je etil ili metil, a R2 je metoksimetil.37. The method according to claim 36, characterized in that R3 is 2,6-dimethylphen-1-yl or 2-methyl-6-ethylphen-1-yl, R1 is ethyl or methyl, and R2 is methoxymethyl. 38. Postupak prema zahtjevu 23, naznačen time, što se dodatno koristi jedna kiselina.38. The method according to claim 23, characterized in that one acid is additionally used. 39. Postupak prema zahtjevu 38, naznačen time, što je kiselina anorganska ili organska kiselina.39. The method according to claim 38, characterized in that the acid is an inorganic or organic acid. 40. Postupak prema zahtjevu 38, naznačen time, što se kiselina koristi u količini od 0.1 do 50 tež. postotaka, temeljeno na nezasićenom organskom spoju.40. The method according to claim 38, characterized in that the acid is used in an amount of 0.1 to 50 wt. percentages, based on the unsaturated organic compound. 41. Postupak prema zahtjevu 39, naznačen time, što je organska kiselina alifatska ili aromatska karboksilna kiselina, sulfonska kiselina ili fosforna(V) kiselina.41. The method according to claim 39, characterized in that the organic acid is an aliphatic or aromatic carboxylic acid, sulfonic acid or phosphoric (V) acid. 42. Postupak prema zahtjevu 39, naznačen time, što je organska kiselina octena kiselina, propionska kiselina, trofluorooctena kiselina, klorooctena kiselina ili metansulfonska kiselina, a anorganska kiselina je H2SO4.42. The method according to claim 39, characterized in that the organic acid is acetic acid, propionic acid, trifluoroacetic acid, chloroacetic acid or methanesulfonic acid, and the inorganic acid is H2SO4. 43. Postupak prema zahtjevu 23, naznačen time, što je molarni odnos nezasićenog organskog spoja prema iridijevom katalizatoru od 500,000 prema 20.43. The method according to claim 23, characterized in that the molar ratio of the unsaturated organic compound to the iridium catalyst is 500,000 to 20. 44. Postupak prema zahtjevu 23, naznačen time, što je temperatura reakcije od -20 do 100° C.44. The method according to claim 23, characterized in that the reaction temperature is from -20 to 100°C. 45. Postupak prema zahtjevu 23, naznačen time, što je pritisak vodika od 5 do 150 bara.45. The method according to claim 23, characterized in that the hydrogen pressure is from 5 to 150 bar. 46. Postupak prema zahtjevu 23, naznačen time, što se hidrogenizira aldimin ili ketimin formiran in situ prije ili za vrijeme hidrogenizacije.46. The method according to claim 23, characterized in that aldimine or ketimine formed in situ before or during hydrogenation is hydrogenated. 47. Katalizator za hidrogenizaciju koji je proizvod reakcije iridijeve(III) ili iridijeve(IV) soli ili njenog hidrata sa difosfinom naznačen time, što ima grupe sekundarnog fosfina i alkalni metal ili amonijev klorid, bromid ili jodid.47. Catalyst for hydrogenation which is the product of the reaction of iridium(III) or iridium(IV) salt or its hydrate with diphosphine characterized by having secondary phosphine groups and alkali metal or ammonium chloride, bromide or iodide. 48. Korištenje kao katalizatora za hidrogenizaciju reakcijskog proizvoda iridijeve(III) ili iridijeve(IV) soli ili njenog hidrata, difosfina naznačeno time, što koji ima grupe sekundarnog fosfina i alkalno metalni ili amonijev klorid, bromid ili jodid.48. Use as a catalyst for the hydrogenation of the reaction product of iridium(III) or iridium(IV) salt or its hydrate, diphosphine characterized by having secondary phosphine groups and alkali metal or ammonium chloride, bromide or iodide.
HR00310/94-6A 1994-02-02 1995-02-01 Hydrogenation catalyst, process for the preparation thereof and hydrogenation process HRP950045A2 (en)

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IL112493A (en) 1999-11-30
WO1995021176A1 (en) 1995-08-10
EP0741738A1 (en) 1996-11-13
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EP0741738B1 (en) 1999-10-13
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AU1575495A (en) 1995-08-21
ZA95780B (en) 1995-08-02
CN1139930A (en) 1997-01-08

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